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Organoantimony(III) compounds containing (imino)aryl ligands of thetype 2-(RN=CH)C

6H

(R = 2!"!"6!-#e

$C

6H

2" 2!"6!-i%r

2C

6H

$)& 'romides

and chalcogenides

na #aria %reda"a"d Ciprian I Ra*"+a Cristian ,ilestru"+a Hans . /reunig"' Heinrich 0ang"c 1o'ias

Rffer

c

and #ichael #ehring+

d

Received (in XXX, XXX) Xth XXXXXXXXX 2009, Accepted Xth XXXXXXXXX 200X

First published on the web Xth XXXXXXXXX 200X

3OI& 4545$7'5555558

The reaction of 2-(RN=CH)C6H4MgBr [R = 2′,4′,6′-Me3C6H2 (R 1), 2′,6′- ir 2C6H3 (R 2)! ["re"are#fro$ 2-(R 1 N=CH)C6H4Br (4) or 2-(R 2 N=CH)C6H4Br (2) an# Mg! %ith &'C3 in 21 an# 11 $oarratio foo%e# '* treat$ent %ith an a+eo .Br otion ga/e [2-(R 1 N=CH)C6H4!2&'Br ($) an#[2-(R 2 N=CH)C6H4!2&'Br () a %e a [2-(R 1 N=CH)C6H4!&'Br 2 (6) an# [2-(R 2 N=CH)C6H4!&'Br 2(9)0 Treat$ent of %ith Na2&H2 "ro/i#e# the #incear [2-(R 2 N=CH)C6H452&'!2& (:)0Heteroc*cic "ecie, i.e. the oi#e cyclo-[2-(R 2 N=CH)C6H45&'!3 (;) an# the fi#e cyclo-[2-

(R 1 N=CH)C6H45&'&!2 () an# cyclo-[2-(R 2 N=CH)C6H45&'&!2 (45) %ere o'taine# '* reacting#i'ro$i#e 6 an# 9 %ith .H an# Na2&H2, re"ecti/e*, in a %ater7toene o/ent $itre0The fi#e 45 reacte# %ith [8(C)9(thf)! to *ie# the hetero$etaic co$"e cyclo-[2-(R 2 N=CH)C6H45&'&!2[8(C)9! (44)0 The co$"on# %ere characterie# '* $tincear NMR"ectroco"* in otion, $a "ectro$etr* an# :R "ectroco"* in the oi# tate0 The $oecartrctre of , :, 6CHC3, 9, CH2C2, 45 an# 44;029CH3H) %ere eta'ihe# '* inge-cr*ta<-ra* #iffraction0 Theoretica cacation ing >T $etho# %ere carrie# ot on 'ro$i#e 9 an#the geo$etrica io$er of it #i$er aociation a %e a the geo$etrica io$er of fi#e 45

an# it $ono$er0

Introduction

The che$itr* of h*"er/aent organoanti$on* co$"on# 1-4

containing one "en#ant ar$ (C,N )-igan# ch a 2-[Me2 NCH(R)!C6H4 [R = H,9 Me9h,6! or 2-[(CH2CH2)2 NCH2!C6H4,? @"incerA-t*"e igan# ie*$$etric 2,6-(Me2 NCH2)2C6H3 [( N,C,N )-igan#!, 2,6-(RCH2)2C6H3 [(O,C,O)-igan#!,e, a*$$etric 2-(Me2 NCH2)-6-(RCH2)C6H3 [( N,C,O)-igan#!,1; orD(CH2C6H4)2 (D = RN, , &) gro",3,4 %hich a can 'econi#ere# a #ianionic (C,E,C )-igan#, raie# in recent *eara coni#era'e interet %ith regar# to 'oth fn#a$entareearch an# a""ication0 &ch igan# can "rotect the $etacentre '* increae# coor#ination throgh intra$oecarDE&' (D = N, , &) interaction o'er/e# 'oth in the oi#tate an# in otion, th "ro/i#ing ther$o#*na$ica

ta'iiFation an# ao%ing ioation of na "ecie, e.g.heteroc*cic organoanti$on* fi#e, (R&'&) 20 H*"er/aent[2,6-(Me2 NCH2)2C6H3&'D!2 (D = , &) can 'e e# to tra"C2 or C&2G thee co$"on# %ere fon# to react re/eri'*%ith C2 or C&2 in otion0f, Io their e a reagent or acata*t in organic *nthei (e.g. cro-co"ingreaction11,12) %a re"orte#0

:n contrat to h*"er/aent organoanti$on* co$"on#containing igan# %ith a sp3-nitrogen ato$ in the "en#antar$, reate# "ecie 'ae# on intra$oecar N( sp2)E&'interaction %ere $ch e in/etigate#0 >or ea$"e [2-RN=CH5C6H4!3&' [R = ( R)-MeC6H4CH(Me), ( R)-

HCH2CH(Dt)!13 %a o'taine# '* con#enation of RNH 2 %ith[2-(=CH)C6H4!3&'014 H*"ercoor#ination intetraar*ti'oni$ at %a reate# to the "reence of aninterna NE&' interaction in [R&'R′3![C:2! [R = 2-(4-MeC6H4 N=CH)C6H4, 2-(3,9-<2-4-HC6H2 N=CH)C6H4 (< =C, Br, h)!19a an# [2-(4-MeC6H4 N=CH)C6H4&'h3!4[C14:1!019' I re$ara'eachie/e$ent %a the ioation of a R&'(:) $ono$er ing the "incer ( N,C,N )-igan# R = 2,6-[2′,6′-Me2C6H3 N=C(Me)!2C6H3016 Recent*, %hie thi %or %an#er "rogre,1? organoanti$on* co$"on# ch aR n&'C3-n (n = 1,2), R 4&'2 an# cyclo-(R&')4 [R = 2-(2′,6′-ir 2C6H3 N=CH)C6H4! %ere re"orte#01

I "art of or interet on organoanti$on*(:::) co$"on#%ith "en#ant ar$ %e re"ort herein the *nthei,

"ectroco"ic characteriFation an# cr*ta trctre of "ecie('ro$i#e an# chacogeni#e) containing (i$ino)ar* igan#of the t*"e 2-(RN=CH)C6H4 (R = 2′,4′,6′-Me3C6H2, 2′,6′-ir 2C6H3)0 The che$itr* of thee co$"on# %ith rigi# an#terica* #e$an#ing organic gro" i co$"are# %ith that ofreate# organoanti$on*(:::) "ecie containing the 2-(Me2 NCH2)C6H4 igan#09g,9i,9

Results and 3iscussion

,ynthesis and characteri<ation of organoantimony(III)'romides

The organic 'ro$i#e 2-(RN=CH)C6H4Br [R = 2′,4′,6′-

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Me3C6H2 (R 1) (4), 2′,6′-ir 2C6H3 (R 2) (2)! %ere o'taine# a E

io$er '* con#enation of 2-'ro$o'enFa#eh*#e %ith thecorre"on#ing aro$atic a$ine accor#ing to a ight*$o#ifie# iteratre $etho# re"orte# for 2 (&che$e 1)01 Bothco$"on# %ere ioate# a *e o% oi# afterrecr*taiFation fro$ heane (9J for 4, ?6J for 2)0Treat$ent of the Krignar# reagent RMgBr %ith &'C 3 in a21 an# 11 $oar ratio ga/e $itre of chori#e7'ro$i#eR 2&'< an# R&'<2 #eri/ati/e, re"ecti/e*, #e to "artiahaogen echange reaction0 >oo%ing treat$ent of the cr#eorganoanti$on* hai#e in CH2C2 %ith an a+eo otion of

.Br the "re 'ro$i#e R 2&'Br an# R&'Br 2 %ere ioate# a*eo% oi# (*ie# in the range 3?- 93J)0 Both the organic 'ro$i#e 4 an# 2 an# the organoanti$on*(:::) 'ro$i#e [2-(R 1 N=CH)C6H4!2&'Br ($) an# [2-(R 2 N=CH)C6H4!2&'Br () a%e a #i'ro$i#e [2-(R 1 N=CH)C6H4!&'Br 2 (6) an# [2-(R 2 N=CH)C6H4!&'Br 2 (9) are %e o'e in chorinate#o/ent (CH2C2, CHC3)0 NMR #ata of 4 L , 6 an# 9 a %ea ee$enta ana*tica #ata are conitent %ith the antici"ate#for$a0 The D: $a "ectra of the organic 'ro$i#e 4 an# 2

ho% the corre"on#ing $oecar ion0 >or the [2-(RN=CH)C6H4!n&'Br 3-n (n = 2, 1) "ecie (co$"on# 2, , 6,9) the 'ae "ea in the D&: $a "ectra are aigne# to[R 2&'! an# [R&'Br ! frag$ent for the $ono'ro$i#e [2-

(RN=CH)C6H4!2&'Br an# #i'ro$i#e [2-(RN=CH)C6H4!&'Br 2, re"ecti/e*0

The NMR "ectra of 4 L , 6 an# 9 %ere recor#e# in CC3

at roo$ te$"eratre0 The aign$ent of reonance in the 1Han# 13C NMR "ectra %a 'ae# on 2 NMR (H&C, HMBCan# C&O) correation "ectra, accor#ing to the n$'eringche$e ho%n in &che$e 20 The "ectra of the #i'ro$i#e 6

an# 9 ho% one et of reonance for the 'titent in ortho

"oition a %e a for the meta "oition of the aro$atic Rgro" attache# to nitrogen, conitent %ith the "reence ofon* one "ecie in otion for %hich free rotation aron# theCLN(=C) inge 'on# i not retricte#0 The "reence of t%o#o'et for the $eth* "roton of the ir gro" in 9 in#icate

their #iatereoto"ic natre0 No eentia change %ereo'er/e# %hen the 1H NMR "ectr$ of 9 %a recor#e# inCC3 at L6; PC0

&ignificant #ifference ho# 'e note# in the otion 'eha/ior of the 'ro$i#e $ an# 0 >or $ 'oth 1H an# 13C NMR "ectra ehi'it on* one et of aro$atic reonance an#one reonance for the imine "roton (δ 02 ""$)0 Thi iconitent %ith e+i/aence of the organic gro" attache# toanti$on* at the NMR ti$e cae, %hich gget a fatfiona 'eha/ior, i.e. coor#ination-#ecoor#ination of thenitrogen ato$0 Moreo/er, the "reence of t%o har"

reonance at δ 1069 an# 202; ""$ (21 integra ratio) aigne#to $eth* "roton in#icate that there i no retriction of freerotation of the $eit* gro" aron# the CLN(=C) inge 'on#0 :t ho# 'e note# that in the cae of the reate# [2-(Me2 NCH2)C6H4!2&'C the #*na$ic "roce reting ine+i/aent organic igan# i froFen on* at L6; PC, %hie atroo$ te$"eratre the 1H NMR "ectr$ ho% one et of 'roa# reonance09g B* contrat, the roo$ te$"eratre NMR"ectra for ho% t%o et of reonance in#icating that theorganic gro" in thi $oece are not e+i/aent a %a aoo'er/e# in the oi# tate (ee 'e+ent #icion) #e tothe coor#ination of nitrogen ato$ trans to 'ro$ine or to an

" | Journal Name& $year%& [vol& ''('' This journal is © The Royal ocie!y o" Che#is!ry $year%

,cheme 4 re"aration of co$"on# 4 L 44

,cheme 2 N$'ering che$e for NMR aign$ent0

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aro$atic car'on attache# to the $eta ato$, re"ecti/e*0 Ii$iar "attern %a ao o'er/e# at roo$ te$"eratre for theanaogo chori#e, [2-(2′,6′-ir 2C6H3 N=CH)C6H4!2&'C01

Thi i cear* e/i#ence# '* the "reence of t%o har" ingetreonance in the aro$atic region, aigne# to the imine

"roton of the non-e+i/aent organic 'titent (δ 036 an#043 ""$, re"ecti/e*)0 Moreo/er, the 1H (ee >igre 1) an#13C NMR (ee D&:, >igre &3 an# &4) "ectra in#icate thatfor one igan# nit (#eignate# '* /) free rotation aron# theCLN(=C) inge 'on# i not retricte# (e.g. one ingetreonance at δ 2?0?? ""$ for C-?′ ato$G &che$e 2') an# forthe other 'titent (#eignate# '* ) the free rotation of the '* 2,6- ir 2C6H3 gro" i 'oce#0 Thi ret in non-e+i/aence of the t%o ha/e of thi aro$atic $oiet*(&che$e 2c) a in#icate#, for ea$"e, '* the "reence of t%oinget reonance at δ 20;; an# 204 ""$ for C-?′a an# C-

?′ ', re"ecti/e*0 The #ifferent 'eha/ior of $ an# in CC3

otion at roo$ te$"eratre $ight 'e reate# to the 'ineof the organic gro" attache# to nitrogen0

The :R tretching /i'ration of the car'onLnitrogen #o'e 'on# a""ear in the 169;L199; c$ L1 region a t*"ica forco$"on# containing &chiff-'ae igan#0 :n the :R "ectraof the tite organoanti$on*(:::) 'ro$i#e the QC =N tretching/i'ration %a o'er/e# at 1624 (for $), 1634 (for ), 161? (for6) an# 1621 c$-1 (for 9), re"ecti/e*0 Thi "attern $ight 'econitent %ith the "reence of intra$oecar NE&'coor#ination an# a #eocaiFation of the eectron of the L C=NL 'on# o/er the reting C3 N&' ring0

&inge cr*ta ita'e for <-ra* #iffraction t#ie %ere

o'taine# '* o% #iffion of n-heane into CH2C2 ( an# 9)or CHC3 (6CHC3) otion0 The oi# tate $oecartrctre of thee 'ro$i#e are #e"icte# in >igre 2-40&eecte# interato$ic #itance an# ange are $$ariFe# inTa'e 1 an# 20

I e"ecte#, a co$$on featre for the oi# tate trctreof the tite co$"on# i that the imine nitrogen i coor#inate#intra$oecar* to the anti$on* ato$0 :n reate# co$"on#%ith "en#ant ar$ %hich contain a sp3-car'on ato$ 'et%eenthe aro$atic ring an# the #onor ato$ [e.g. 2-[Me2 NCH(R)!C6H4, 2-[(CH2CH2)2 NCH2!C6H4, 2,6-(RCH2)2C6H3! a fi/e-$e$'ere# C3&'D cheate ring %ith

interna DE&' (D = N, ) interaction ret0 Thi ring ifo#e# aong the &'C$eth*ene ai an# thi in#ce "anarchirait*04,9 :n contrat, the "reence of the LC=NL 'on# in the "en#ant ar$ ret in a "anar C3&'N nit an# th, the titeco$"on# #o not an*$ore ehi'it "anar chirait*0 Ho%e/er,the intra$oecar N( sp2)E&' interaction ret in @chelate

induced-Sb-chiral A co$"on#04,9 The organic igan# in

'eco$e non-e+i/aent ince the nitrogen ato$ arecoor#inate# to anti$on* trans to #ifferent ato$0 &i$iar*, in6 an# 9 the t%o haogen ato$ "er $oece are not e+i/aent


ig 4 1H NMR "ectr$ (CC3, 3;; MHF) of co$"on# , at roo$ te$"eratre0

1a'le 4 &eecte# 'on# #itance (S) an# ange (P) for co$"on# an#:

:&'(1)LC(1) 20169(9) 2016?(2)&'(1)LC(2;) 20193(9) 20163(2)&'(1)LD(1)a 2063?1(11) 204?2?(6)&'(1)LN(1) 204(4) 20616(2)&'(1)LN(2) 206(4)

N(1)LC(?) 102??(6) 102??(3) N(1)LC() 10444(6) 10432(3) N(2)LC(26) 10292(?) 10264(3) N(2)LC(2?) 10423(6) 10432(3)

C(1)L&'(1)LC(2;) 904(1) 1;10;;()D(1)L&'(1)LC(1) 3019(14) ?0;1(9)D(1)L&'(1)LC(2;) ;0(13) 10??(9) N(1)L&'(1)LC(1) ?202(1?) ?101(?) N(1)L&'(1)LC(2;) 6043(16) 3066(6)

N(1)L&'(1)LD(1) 169043(1;) 166014(3) N(1)L&'(1)LN(2) 1;20;;(13) N(2)L&'(1)LC(1) 1630?9(16) N(2)L&'(1)LC(2;) 602;(16) N(2)L&'(1)LD(1) ;024()

&'(1)LD(1)L&'(1a) 09?(3)

C(?)LN(1)LC() 11?06(4) 1101(1?)&'(1)LN(1)LC(?) 1;02(3) 1;602(1)&'(1)LN(1)LC() 13;01(3) 12606(1)

C(26)LN(2)LC(2?) 110(9) 1106(1)&'(1)LN(2)LC(26) 04(4)&'(1)LN(2)LC(2?) 14;06(3)

a D(1) = Br(1) for , an# &(1) for :G ' &*$$etr* e+i/aent ato$ ( !, y,".#$ ) are gi/en '* @aA0

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foo%ing the coor#ination of the nitrogen in trans "oition toone of the$0 :n 'oth #iorgano- an# $onoorganoanti$on*(:::)

#eri/ati/e the chirait* th in#ce# at the $eta ato$ can 'e#ecri'e# in ter$ of C &' an# %&' io$er2; for the +are "*ra$i#a (C,N )2&'Br (h*"er/aent 12-&'-9 "ecie) an# pseudo-trigona 'i"*ra$i#a (@ see-sa&A) (C,N )&'Br 2 core(h*"er/aent 1;-&'-4 "ecie), re"ecti/e*01,21 :n#ee#, thecr*ta of the tite 'ro$i#e contain a 11 $itre of theeio$er0

I e"ecte#, in the 'ro$i#e the trength of the interna NE&' interaction i #ifferent, i.e. that one eta'ihe# trans

to the 'ro$ine ato$ [&'(1)LN(1) 204(4) SG N(1)L&'(1)L Br(1) 169043(1;)P! 'eing tronger than that one eta'ihe#trans to the car'on ato$ [&'(1)LN(2) 206(4) SG N(2)L &'(1)LC(1) 1630?9(16)PG c'. $ of the corre"on#ing

co/aent, r co/(&',N) 2011 S, an# /an #er 8aa ra#ii,r /#8(&',N) 30?4 S!022 The ength of thee NE&' 'on# arei$iar to thoe re"orte# for the anaogo chori#e [&'(1)L N(1) 20416(2) SG &'(1)LN(2) 2092(3) S!0 8hen co$"are# tothe NE&' interaction in the reate# [2-(Me2 NCH2)C6H4!2&'Br [&'(1)LN(1) 20423(3) SG &'(1)LN(2)302?6(3) S!9g the ignificant #ecreae of the interato$ic#itance corre"on#ing to the NE&' interaction trans to thecar'on ato$ i re$ara'e0 Thi 'eha/ior i a cone+enceof the 'etter #onor "ro"ertie of a N( sp2) ato$ (ersus a N( sp3)ato$0

The anti$on*-nitrogen #itance in the #i'ro$i#e 6 [&'(1)L N(1) 20346(3) S! an# 9 [&'(1)LN(1) 2039(3) S! i horter

than in 0 Thi i a ret of a co$'ine# effect "ro#ce# '*the h*'ri#iFation natre of the #onor ato$ [N( sp2)! an# theincreae# Ue%i aci#it* of the $eta ato$ %ith increaingn$'er of haogen ato$ attache# to it [to 'e co$"are# %ith[2-(Me2 NCH2)C6H4!&'Br 29g &'(1)LN(1) 204;(3) S!0

8hie no inter$oecar interaction 'et%een hea/* ato$%ere o'er/e# in the 'ro$i#e , the $oece of the#i'ro$i#e are aociate# into centro*$$etric #i$er nit 'it fro$ C &' an# %&' io$er throgh a*$$etric 'ro$ine 'ri#ge in/o/ing the haogen trans to nitrogen (>igre 3 an#4)0 I e"ecte#, for the $oecar nit of the #i'ro$i#e 6

an# 9 the ter$ina &'LBr 'on# i $ch horter than that

in/o/e# in the 'ro$ine &'LBr&' 'ri#ge, %hie the &'LBr 'on# in i of inter$e#iate ength 'et%een the /aeo'er/e# for the #i'ro$i#e (ee Ta'e 1 an# 2)0 The o/eracoor#ination geo$etr* aron# the $eta 'eco$e +are "*ra$i#a [(C,N )&'Br 3 core! in 6 an# 9 if the inter$oecaranti$on*-'ro$ine interaction [&'(1)LBr(1a) 302;9;(9) S for6 an# 303362(9) S for 9, re"ecti/e*! i taen into accont(h*"er/aent 12-&'-9 "ecie)01,21 :t ho# 'e note# the trans

orientation of the &'LC, ter$ina &'LBr an# &'LN 'on# ofthe t%o $oece in the #i$er nit %ith re"ect to the centra "anar &'2Br 2 ring (ee ao the Theoretica Cacation

ection)0 I i$iar a*$$etric #i$er aociation %a#ecri'e# for the reate# [2-(Me2 NCH2)C6H4!&'Br 209g :ncontrat, the cr*ta of the chori#e anaoge, [2-(2′,6′-ir 2C6H3 N=CH)C6H4!&'C2, %a re"orte# to contain on*#icrete $oece, %ithot inter$oecar interaction 'et%een hea/* ato$01

:ntra$oecar BrH contact are eta'ihe# in the$oece of [Br(1)H(6)ar* 201 SG Br(1)H(36)$ethine 209S!0 :n a##ition, a coer oo re/eae# 'oth intra- an#inter$oecar C H‒ (hcentroi#) #itance conitent %ith interaction 'et%een h*#rogen ato$ of one ir gro" an# thearo$atic ring attache# to the $eta (i.e. Hhcentroi# contacthorter than 301 S, %ith an ange V 'et%een the nor$a to the

# | Journal Name& $year%& [vol& ''('' This journal is © The Royal ocie!y o" Che#is!ry $year%

ig 2 RTD re"reentation at 3;J "ro'a'iit* an# ato$ n$'eringche$e for the (C &')- io$er0

ig RTD re"reentation at 4;J "ro'a'iit* an# ato$ n$'eringche$e for the #i$er aociation 'et%een (C &')- an# ( %&')-9 io$er inthe cr*ta of 9 [*$$etr* e+i/aent ato$ ()!, )y, )$ ) are gi/en '*

@"ri$eA!0

ig $ RTD re"reentation at 4;J "ro'a'iit* an# ato$ n$'eringche$e for the #i$er aociation 'et%een (C &')- an# ( %&')-6 io$er inthe cr*ta of 6CHC3 (o/ent $oece i not ho%n) [*$$etr*e+i/aent ato$ (2!, y, )$ ) are gi/en '* @"ri$eA!0

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aro$atic ring an# the ine #efine# '* the H ato$ an# hcentroi#

$aer than 3;P)23 C(1?)‒H(1?)$ethinehcentroi#C(2;)-C(29)5204 S, V = 104P, an# C(1)‒H(1C)$eth*hcentroi#C(1a)-C(6a)5 20?6 S, V = 0?P0 The atter one ret in the for$ationof "o*$eric chain of (C &')- an# ( %&')- io$er,

re"ecti/e*, %ithot frther contact 'et%een "arae chain(for #etai, ee D&:)0WI in the cae of the $ono'ro$i#e , an intra$oecar

BrH contact i eta'ihe# in the $oece of 6 or 9

[Br(1)H(6)ar* 20; S!0 :n a##ition, frther BrH contactare eta'ihe# 'et%een the t%o ha/e of the centro*$$etric#i$er nit [Br(1)H(16I′)$eth* 301; S in 6GBr(1)H(14′)$ethine 203 S in 9!0 :n the cr*ta of 6CHC3 the#i$er nit are connecte# throgh %ea C H‒ (hcentroi#)interaction [C(19)‒H(19C)$eth*hcentroi#C(′a)-C(13′a)520 S, V = 2401P! into chain "o*$er of aternating (C &')-an# ( %&')-6 io$er0 Dach chain i frther connecte# to otherfor "arae chain throgh %ea BrH contact

[Br(2)H(?)i$ine 30;9 S! %hich in/o/e the ter$ina 'ro$ineato$ of the #i$er nit0 B* contrat, the cr*ta of 9 containa*er in %hich a #i$er nit i connecte# to other for #i$erthrogh C H‒ (hcentroi#) [C(3)‒H(3)ar*hcentroi#C(a)-C(13a)5 202 S, V = 1304P! an# BrH [Br(2a)H(16B)$eth*

206 S! contact (for #etai, ee D&:)0W

,ynthesis and characteri<ation of organoantimony(III)chalcogenides

The *nthei of organoanti$on*(:::) chacogeni#e %a 'ae# on "re/io* #e/eo"e# $ie#-o/ent "roce#re, 9i,9

i.e. reaction of 9 %ith .H or the 'ro$i#e , 6 or 9 %ith Na2&H2, in %ater7toene $itre (&che$e 1)0 The

co$"on# %ere ioate# a coore (oi#e ;) or *eo% toorange oi# (fi#e :, , 45)0 Treat$ent of the heteroc*cicfi#e 45 %ith [8(C)9(thf)! in 11 $oar ratio ga/e the$eta car'on* co$"e cyclo-[2-(2′,6′-ir 2C6H3 N=CH)C6H45&'&!2[8(C)9! (44) a an orange-'ro%n

oi#0 The :R 'an# in the range 161 L 162 c$ L1

areaigne# to the QC =N tretching /i'ration, %hich i conitent%ith the "reence of the i$ine igan# in the tit echacogeni#e0 The :R "ectr$ of 44 ho% the t*"ica "attern for co$"ee containing a 8(C) 9 frag$ent0 The$oecar ion [M! %a o'er/e# in the D: M& of cyclo-[2-(2′,4′,6′-Me3C6H2 N=CH)C6H45&'&!2 () 0 The D&: $a"ectra of cyclo-[2-(R 2 N=CH)C6H45&'!3 (;) an# cyclo-[2-(R 2 N=CH)C6H45&'&!2 (45) (R 2 = 2′,6′-ir 2C6H3) ho% thecorre"on#ing $oecar [M H! ion, %hie for [2-(2′,6′-ir 2C6H3 N=CH)C6H452&'!2& (:) the ion [M X H! %ao'er/e#0 >or the co$"e 44 a [M - C! ion %a aigne# tothe 'ae "ea0

The1

H an#13

C NMR "ectra, recor#e# in CC3 at roo$te$"eratre, "ro/i#e e/i#ence for o$e "articar 'eha/iorin otion for thee chacogeni#e0 The aign$ent ofreonance %a 'ae# on 2 NMR (H&C, HMBC an#C&O) correation "ectra, accor#ing to the n$'eringche$e ho%n in &che$e 20 The 1H NMR "ectr$ of thefi#e : ho% on* one et of 'roa# reonance, inc#ingthat for the imine "roton (δ 034 ""$)0 Thi 'eha/iorgget a +ite fat #*na$ic "roce on the NMR ti$e caeto gi/e for e+i/aent organic gro" attache# to anti$on*ato$ in thi #incear "ecie0 I i$iar otion 'eha/ior%a "re/io* #ecri'e# for the reate# co$"on# [2-(Me2 NCH2)C6H452&'!2&09

This journal is © The Royal ocie!y o" Che#is!ry $year% Journal Name& $year%& [vol& ''('' | $

1a'le 2 &eecte# 'on# #itance (S) an# ange (P) for co$"on# 6CHC3, 9, CH2C2 an# 45

6CHC3 9 CH2C2 45

&'(1)LC(1) 2014(3) 20162(3) &'(1)LC(1) 20161(3) 20162(4)&'(1)LBr(1) 20;34(9) 20?1?4(?) &'(1)L&(1) 209326() 20926()&'(1)LBr(2) 209?4(9) 209426(?) &'(1)L&(1′) 204;16()c 20416?(1;)#

&'(1)LN(1) 20346(3) 2039(3) &'(1)LN(1) 20993(2) 2099(2)

&'(1)LBr(1′) 302;9;(9)a

303362(9) '

N(1)LC(?) 1029(9) 1023(3) N(1)LC(?) 10264(4) 10261(4) N(1)LC() 10432(9) 10432(4) N(1)LC() 10436(4) 10436(4)

C(1)L&'(1)LBr(1) ;0?;(1;) 106() C(1)L&'(1)L&(1) 90;() 403?()C(1)L&'(1)LBr(2) 2042(11) 3016() C(1)L&'(1)L&(1′) 1;;019() 094()Br(1)L&'(1)LBr(2) ?014(1) 061(1) &(1)L&'(1)L&(1′) 06(3) 0;(3) N(1)L&'(1)LC(1) ?9049(12) ?404(1;) N(1)L&'(1)LC(1) ?2029(1;) ?203(11) N(1)L&'(1)LBr(1) 16306;(?) 16402(9) N(1)L&'(1)L&(1) 1610(6) 161096(6) N(1)L&'(1)LBr(2) 40?6(?) 30?(6) N(1)L&'(1)L&(1′) 1012(6) ;02(6)Br(1′)L&'(1)LC(1) ;099(11) ??061(?)Br(1′)L&'(1)LBr(1) ?093(1) 10?6(1)Br(1′)L&'(1)LBr(2) 1?1012(1) 1?;0?;(1)Br(1′)L&'(1)LN(1) 09(?) 2044(6)

&'(1)LBr(1′)L&'(1′) 204?(1) 024(1) &'(1)L&(1′)L&'(1′) 1031(3) ;03(3)C(?)LN(1)LC() 12;0(3) 12;0(3) C(?)LN(1)LC() 12;04(3) 1103(3)&'(1)LN(1)LC(?) 1110?(2) 11102(2) &'(1)LN(1)LC(?) 1;0;;(1) 1;0(2)&'(1)LN(1)LC() 12?0;(2) 12?0(1?) &'(1)LN(1)LC() 13;06;(1) 13102(2)

a &*$$etr* e+i/aent ato$ (2!, y, )$ ) are gi/en '* @"ri$eAG ' &*$$etr* e+i/aent ato$ ()!, )y, )$ ) are gi/en '* @"ri$eAG c &*$$etr*e+i/aent ato$ ()!, y, $ ) are gi/en '* @"ri$eAG # &*$$etr* e+i/aent ato$ ( !, y, 2$ ) are gi/en '* @"ri$eA0

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The 1H an# 13C NMR "ectra of the oi#e ; ho% t%o etof reonance0 8hie the 1H reonance in the ai"hatic regionare not %e e"arate#, thoe in the aro$atic region in#icate a21 integra ratio for e+i/aent "roton, e.g. δ 039 (2 H) an#036 (1 H) ""$ for imine "roton0 Thi gget the "reenceof a tri$er "ecie in otion, %ith cis an# trans organic'titent %ith re"ect to a &' 33 heteroc*ce0 I tri$er"ecie i conitent %ith the $oecar [M H! iono'er/e# in the D&: $a "ectr$ of ;0 :t ho# 'e note#

that a i$iar 'eha/ior in otion %a re"orte# for theorganic gro" in cyclo-[2-(Me2 NCH2)C6H45&'!3, for%hich the tri$eric natre %a ao eta'ihe# '* inge-cr*ta <-ra* trctre ana*i0 9i

>or 'oth heteroc*cic fi#e an# 45 the NMR "ectra (inCC3, at r0t0) contain t%o et of reonance igna 'oth inthe a* an# ar* region0 The corre"on#ing integra ratio 'ae# on the reonance for the H-6 (for ) an# H-4 (for 45) "roton (ee &che$e 2) i 1041 an# 101, re"ecti/e*0 Noignificant change %ere o'er/e# %hen the 1H NMR"ectr$ of %a recor#e# in CC3 at L6; PC0 Taing intoaccont the ret o'taine# '* inge-cr*ta <-ra*#iffraction (ee 'e+ent #icion) an# the 'eha/ior in

otion %hich gget the a'ence of ringLring e+ii'ria, it$ight 'e conc#e# that the oigo$eriFation #egree o'er/e#in oi# tate, i.e. #i$er "ecie, i "reer/e# in chorofor$otion0 I i$iar itation %a re"orte# "re/io* for thereate# cyclo-[2-(Me2 NCH2)C6H45&'&!209i &e/era io$ercan 'e then coni#ere# for fi#e of the t*"e cyclo-[2-(RN=CH)C6H45&'&!2 %ith the reati/e orientation of the &'‒C an# &'LN 'on#, i.e. all -trans, trans-&' C7‒ cis-&'LN, cis-&' C7‒ trans-&'LN, an# all -cis, re"ecti/e*, %ith re"ect to a&'2&2 ring (&che$e 3)0 Ithogh the t%o et of reonanceco# not 'e aigne# to a "articar io$er, one can a$ethat the all -trans an# all -cis io$er (ee 'e+ent#icion on co$"on# 44) are $ot ie* to 'e "reent in

the chorofor$ otion of the cyclo-[2-(RN=CH)C6H45&'&!2

#eri/ati/e0The 1H NMR "ectr$ of the $eta car'on* co$"e 44

ho% one et of 'roa# inget or "oor reo/e# $ti"et,conitent %ith e+i/aent organic igan# attache# to theanti$on* ato$ an# a #*na$ic "roce at roo$ te$"eratre0The n$'er of 13C reonance aigne# to ai"hatic car'onan# the 'roa# igna for the C-3′ aro$atic car'on gget that

the free rotation aron# the CLN(=C) inge 'on# i retricte#0The "reence of the 8(C)9 $oiet* i in#icate# '* a ingetreonance rron#e# '* 138 ateite, aigne# to thee+atoria C gro"0

&inge cr*ta of :, CH2C2 an# 45 %ere o'taine# '*o% #iffion of n-heane into CH2C2 otion0 Cr*ta of44;029CH3H %ere i$iar* gro%n ing a n-heane-CH2C2

*te$ (31) ($ethano %a e# a ta'iiFing agent for$eth*ene chori#e)0The oi# tate $oecar trctre ofthee fi#e are #e"icte# in >igre 9-0 &eecte#interato$ic #itance an# ange are ite# in Ta'e 1 (for :),2 (for CH2C2 an# 45) an# 3 (44;029CH3H)0

:n contrat to the 'ro$i#e e# a tarting $ateria to

"re"are :, the fi#e ehi'it on* one interna NE&'interaction "er $eta ato$, "ace# trans to the &'-& 'on#[N(1)L&'(1)L&(1) 166014(3)P! (>ig0 9)0 The "en#ant ar$ ofthe econ# organic igan# attache# to the anti$on* ato$ it%ite# to 'ring the nitrogen ato$ N(2) a far a "oi'e fro$the $eta0 The anti$on*-nitrogen #itance i inter$e#iate[N(1)L&'(1) 20616(2) S! 'et%een thoe o'er/e# in the$oece of (Ta'e 1) an# coni#era'* horter than thehortet NE&' interaction [2099(3) S! in [2-(Me2 NCH2)C6H452&'!2&09 The ret i a pseudo-trigona 'i"*ra$i#a coor#ination en/iron$ent for anti$on* in :

[(C,N )C&'& coreG h*"er/aent 1;-&'-4 "ecie!01,21 Thi 'eha/ior i cear* #e to the teric tre "ro#ce# '* the

% | Journal Name& $year%& [vol& ''('' This journal is © The Royal ocie!y o" Che#is!ry $year%

,cheme $ otentia geo$etric io$er for the heteroc*cic fi#e 45 %ith re"ect to a "anar &'2&2 ring0

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&'(1)L&(1)L&'(1′) ange [09?(3)P! %hich 'ring the '*[2-(2′,6′-ir 2C6H3 N=CH)C6H452&'! $oietie in coe "roi$it*0 :t ho# 'e note# that the anti$on*-fr 'on##itance are i$iar in the $oece of : [&'(1)L&(1)204?2?(6) S! an# the reate# [2-(Me2 NCH2)C6H452&'!2&[&'(1)L&(1) 204621(1;) S!, 't the &'(1)L&(1)L&'(1′) ange in

the atter "ecie i $ch $ore o"ene# [1;;0?(9)P!0 >or [2-(Me2 NCH2)C6H452&'!2& thi ao% a +are "*ra$i#a(C,N )2&'& core for 'oth $eta ato$ to %hich, in a##ition,e '* organic igan# are attache#09

>or 'oth heteroc*cic fi#e the cr*ta contain on*#icrete #incear nit of the all -trans ( %&',C &'′)- (>ig0 6)an# (C &', %&'′)-45 (>ig0 ?) io$er %ith a cr*taogra"hica*i$"oe# in/erion *$$etr*0 The o/era $oecar trctreare /er* i$iar to that #ecri'e# for the reate# cyclo-[2-(Me2 NCH2)C6H45&'&!209i The $oece contain a centra, "anar for-$e$'ere# &'2&2 ring, %ith en#oc*cic ange atanti$on* an# fr ato$ coe to ;P (Ta'e 2)0 :n the$oecar nit the ( N,C )-igan# are "ace# on o""oite i#e

of the &'2&2 ring0 The a*$$etr* of the ring i refecte# inaternating hort [&'(1)L&(1′) 204;16() an# 20416?(1;) S for an# 45, re"ecti/e*! an# ong [&'(1)L&(1) 209326() an#20926() S for an# 45, re"ecti/e*! anti$on*-fr 'on#0 The coor#ination of a nitrogen ato$ trans to eachfr ato$ accont for the eongation of the corre"on#ing

anti$on*-fr 'on#0 I e"ecte# for a N( sp2

) #onor ato$,the &'(1)LN(1) 'on# #itance [20993(2) an# 2099(2) S for

an# 45, re"ecti/e*! i horter than that o'er/e# for a N( sp3)#onor ato$ in cyclo-[2-(Me2 NCH2)C6H45&'&!2 [&'(1)LN(1)20634(4) S!09i

8hie the reaction of cyclo-[(Me3&i)2CH&'&!n (n = 2, 3)an# [8(C)9(thf)! ga/e the co$"e cyclo-[(Me3&i)2CH&'&!2[8(C)9!2 %ith $eta car'on* nitcoor#inate# to the &' ato$, 24 the co$"e 44 %a fon# tocontain a 8(C)9 frag$ent coor#inate# to a fr ato$ a inthe reate# cyclo-[2-(Me2 NCH2)C6H45&'&!2[8(C)9!09i

Ho%e/er there i an i$"ortant #ifference in the $oecartrctre of thee 11 a##ct0 :n cyclo-[2-

This journal is © The Royal ocie!y o" Che#is!ry $year% Journal Name& $year%& [vol& ''('' | &

ig 9 RTD re"reentation at 4;J "ro'a'iit* an# ato$ n$'eringche$e for the (C &', %&'′)-45 io$er [*$$etr* e+i/aent ato$ ( !, y,

2$ ) are gi/en '* @"ri$eA!0

ig : RTD re"reentation at 3;J "ro'a'iit* an# ato$ n$'eringche$e for the (C &',C &'′)-: io$er [*$$etr* e+i/aent ato$ ( !, y,

".#$ ) are gi/en '* @"ri$eA!0

ig 6 RTD re"reentation at 4;J "ro'a'iit* an# ato$ n$'eringche$e for the ( %&',C &'′)- io$er [*$$etr* e+i/aent ato$ ()!, y,

$ ) are gi/en '* @"ri$eA!0

ig ; RTD re"reentation at 4;J "ro'a'iit* an# ato$ n$'eringche$e for the (C &'1, %&'2)-44 io$er0

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(Me2 NCH2)C6H45&'&!2[8(C)9! the $eta car'on* nit icoor#inate# to the cis-&' C7‒ trans-&'LN io$er of theheteroc*cic fi#e09i :n contrat, in the $oece of theco$"e 44 a 8(C)9 frag$ent i coor#inate# to the all -cis

io$er of the fi#e 45 (>ig0 ), occ"*ing a trans "oitionreati/e to the organic igan# %ith re"ect to the &' 2&2 ring0Both nitrogen ato$ are coor#inate# to anti$on* ato$ trans

to &(1) %hich i 'e+ent* coor#inate# to tngten0 ne ofthe $aor ret i the #ifferent e+ence of &'L& 'on#

%ithin the &'2&2 ring, i.e. aternating hort an# ong 'on# incyclo-[2-(Me2 NCH2)C6H45&'&!2[8(C)9!, %hie in 44 the&(1) ato$ i in/o/e# in onger 'on# [&'(1)L&(1) 209923()SG &'(2)L&(1) 20994() S! than &(2) ato$ [&'(1)L&(2)204436() SG &'(2)L&(2) 204914() S!0 :t ho# ao 'e note#that the centra for-$e$'ere# &'2&2 ring i ight* fo#e#[fo# ange &(1)&'(1)&(2)7&(1)&'(2)&(2) 60,&'(1)&(1)&'(2)7&'(1)&(2)&'(2) ?01P! an# the en#oc*cicange at fr ato$ are ignificant* #ifferent (Ta'e 3)0

The all -cis orientation of the &' C an# &'‒ LN 'on# %ithre"ect to the &'2&2 ring i $ot ie* a cone+ence of theteric train #e to the '* 'titent on nitrogen0 Thi

ao e"ain the "reence of ece/* all -trans an# all -cis

io$er in the chorofor$ otion of 45 (ee the a'o/e#icion of the NMR "ectra)0

:ntra$oecar &H contact, %hich in/o/e the h*#rogenato$ in ortho "oition of the ar* ring 'on# to anti$on*, areeta'ihe# in the $oece of a fi#e #ecri'e# here0 Theheteroc*cic "ecie an# 45 ho% frther intra$oecar

&Ha* contact [&(1)H(14C′)$eth* 20? S for G&(1)H(1?′)$ethine 209 S for 45!0 >or the $oece of thefi#e : a##itiona intra$oecar C‒H (hcentroi#) contactare "reent [C(9)‒H(9)ar*hcentroi#C(2?′)-C(32′)5 20?1 S, V= 604PG C(1?)‒H(1?)$ethinehcentroi#C(2;′)-C(29′)5 209 S, V= 160;P!0

Ithogh no inter$oecar interaction 'et%een hea/*ato$ %ere fon# in the cr*ta of :, CH2C2, 45 an#44;029CH3H, a coer in"ection re/eae# "ra$oecararchitectre 'ae# on fr-h*#rogen or C‒H (hcentroi#)contact023 Th, in the cr*ta of : a*er of (C &',C &')- an#( %&', %&')-: io$er, re"ecti/e*, are for$e# throghinter$oecar C H‒ (hcentroi#) interaction [C(11)‒

H(11)ar*hcentroi#C(2?′c)-C(32′c)5 202 S, V = 190?P!, 'tno frther contact 'et%een aternating "arae a*er areeta'ihe# (for #etai, ee D&:)0W

>or the heteroc*cic "ecie CH2C2 an# 45 #ifferent"ra$oecar arrange$ent are eta'ihe# in the cr*ta0o*$er chain of ( %&',C &'′)- io$er are for$e# 'ae# on%ea fr-h*#rogen contact [&(1)H(14Ba)$eth* 30;; S!%ith no frther contact 'et%een "arae chain0 &i$iar achain "o*$er of (C &', %&'′)-45 i for$e# 'ae# on C‒H>>>(hcentroi#) contact [C(4)‒H(4)ar*hcentroi#C(')-C(13')520?3 S, V = 1102P!0 >rther contact of a$e t*"e connect "arae chain into a*er [C(1)‒H(1C)$eth*hcentroi#C(′#)-C(13′#)5 201 S, V = 302P! an#

"arae a*er into a 3 architectre, re"ecti/e* [C(19)‒H(19I)$eth*hcentroi#C(1′e)-C(6′e)5 20?? S, V = 110P! (for#etai, ee D&:)0W

i$er aociation are for$e# in the cr*ta of44;029CH3H throgh %ea fr-h*#rogen [&(2)H(4′)ar*

30;2 S! an# +ite trong C‒H>>> (hcentroi#) contact [C(3)‒H(3)ar*hcentroi#C(2;′)-C(29′)5 202 S, V = 601P!0 >rther%ea H [(1)H(12′a)ar* 2096 S, (9)H(26')i$ine 204S! contact an# trong C‒H>>> (hcentroi#) [C(1)‒H(1B)$eth*hcentroi#C(′a)-C(13′a)5 209 S, V = 903P!connect the #i$er into a "o*$er (for #etai, ee D&:)0W

1heoretical calculations

Theoretica cacation ing >T $etho# (eeD"eri$enta &ection for frther #etai) %ere carrie# ot inor#er to in/etigate the geo$etrica io$er of the #i$eraociation of 9 an# the geo$etrica io$er of 450Co$"arion of eecte# cacate# an# #eter$ine# 'on#ength an# ange are "ro/i#e# in D&:, Ta'e &1 an# &20 I/ia co$"arion of the cacate# an# #eter$ine# trctreare ho%n in D&:, >igre &26 an# &2?0

The cacate# geo$etrie re"ro#ce# to a great etent thetrctre #eter$ine# '* inge cr*ta <-ra* #iffractionana*i0 :n the cae of the all -trans #i$er aociation of 9 a#ifference arger than 1;J %a fon# for the Br(1′)X&'(1)

' | Journal Name& $year%& [vol& ''('' This journal is © The Royal ocie!y o" Che#is!ry $year%

1a'le $ &eecte# 'on# #itance (S) an# ange (P) for 44;029CH3H

&'(1)LC(1) 20199(3) &'(2)LC(2;) 201?3(3)&'(1)L&(1) 209923() &'(2)L&(1) 20994()&'(1)L&(2) 204436() &'(2)L&(2) 204914()&'(1)LN(1) 2092(3) &'(2)LN(1) 204?;(3)

N(1)LC(?) 102;(9) N(2)LC(26) 102?3(9)

N(1)LC() 10443(4) N(2)LC(2?) 1043?(9)

8(1)L&(1) 206;;9()8(1)LC(3) 20;36(4) C(3)L(1) 1014(9)8(1)LC(4;) 20;96(4) C(4;)L(2) 10136(9)8(1)LC(41) 20;3(4) C(41)L(3) 1014(9)8(1)LC(42) 20;91(4) C(42)L(4) 10141(9)8(1)LC(43) 1099(4) C(43)L(9) 1019(9)

C(1)L&'(1)L&(1) 4011(1;) C(2;)L&'(2)L&(1) 209()C(1)L&'(1)L&(2) 60;;(1;) C(2;)L&'(2)L&(2) 1;2029()&(1)L&'(1)L&(2) 0?(3) &(1)L&'(2)L&(2) 049(3) N(1)L&'(1)LC(1) ?309(12) N(2)L&'(2)LC(2;) ?304?(11) N(1)L&'(1)L&(1) 166013(?) N(2)L&'(2)L&(1) 16;064(?) N(1)L&'(1)L&(2) 6023(6) N(2)L&'(2)L&(2) 103(?)

&'(1)L&(1)L&'(2) 064(3) &'(1)L&(2)L&'(2) 30?;(3)C(?)LN(1)LC() 1109(3) C(26)LN(2)LC(2?) 12;0(3)&'(1)LN(1)LC(?) 1;?01(2) &'(2)LN(2)LC(26) 11;01(2)&'(1)LN(1)LC() 12603(2) &'(2)LN(2)LC(2?) 12?0(2)

&'(1)L&(1)L8(1) 1;10(3) &'(2)L&(1)L8(1) 1;20?6(3)

&(1)L8(1)LC(3) 202(12) &(1)L8(1)LC(42) 10;1(12)&(1)L8(1)LC(4;) 204(11) &(1)L8(1)LC(43) 1??063(12)&(1)L8(1)LC(41) 1014(11)

C(3)L8(1)LC(4;) ;06(14) C(4;)L8(1)LC(42) 1?90;6(16)C(3)L8(1)LC(41) 1?906(16) C(4;)L8(1)LC(43) 90?(14)C(3)L8(1)LC(42) 2022(16) C(41)L8(1)LC(42) 906(14)C(3)L8(1)LC(43) 902(16) C(41)L8(1)LC(43) ;01(16)C(4;)L8(1)LC(41) ;06(12) C(42)L8(1)LC(43) ;04(19)

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'on# ength0 Thi gget that the inter$oecar 'on#trength at thi e/e of theor* %a o/ereti$ate#0 The engthof the &'XN 'on# %a ao o/ereti$ate# '* 90J, an#cone+ent*, the BrX&' 'on# trans to N %a eongate# '* thea$e a$ont0 The 'on#ing ange aron# anti$on* %ereight* 'etter #ecri'e# than the 'on# ength0 The arget#ifference, of 90J, %a fon# for the C(1)X&'(1)XBr(2) 'on#

ange0The cacate# an# #eter$ine# 'on# ength for the all -

trans io$er of the fi#e 45 are in 'etter agree$ent than inthe #i$er aociation of the #i'ro$i#e 90 >or all -trans-45

io$er the arget #ifference, of 30 an# 30J, %ere fon#for t%o of the &'X& 'on# ength0 The cacate# CX&'X&ange %ere 30J arger than thoe #eter$ine#0

Theoretica cacation re/ea that the coor#ination of thenitrogen ato$ to the anti$on* 'ring a ta'iiFation of 4902Y7$o in 9 an# of ?60? Y7$o in the $ono$er of 450i$eriFation energ* of 9, coni#ering the for$ation of all-

trans io$er, %a fon# to 'e ;01 Y7$o0 iociation of theall-trans io$er of 45 into $ono$er a$ont 19204 Y7$o0

The cacate# reati/e energ* #ifference 'et%eengeo$etrica io$er of the #i$er aociation of 9 an# 'et%eenthe io$er of 45, re"ecti/e*, are /er* $a0 The io$erfon# to ha/e the o%et energ* '* theoretica cacation are#ifferent fro$ thoe fon# in the cr*ta0 Thi i $ot ie* aret of "acing force in the oi# tate0 The energie oftrans-&'XC 7 cis-&'XN, all-trans, an# all-cis io$er of 9 arearger than the energ* of cis-&'XC 7 trans-&'XN io$er %ith101, 4, an# 09 Y7$o, re"ecti/e*0 >or 45 the theoretica #ataho% trans-&'XC 7 cis-&'XN io$er a 'eing the $ot ta'eone0 The energie of the all-trans, cis-&'XC 7 trans-&'XN, an#all -cis io$er of 45 are %ith 10, 40, an# 60 Y7$o arger0

Conclusions

The rigi#it* in#ce# '* the "reence of the C=N 'on# in the "en#ant ar$ an# the terica* #e$an#ing gro" attache# tonitrogen in (i$ino)ar* igan# of the t*"e 2-(RN=CH)C6H4 (R= 2′,4′,6′-Me3C6H2, 2′,6′-ir 2C6H3) %ere e"ecte# to infenceignificant* the otion 'eha/ior an# hence the trctre ofthe corre"on#ing organoanti$on* co$"on#0 The che$itr*of the tite organoanti$on* "ecie containing [2-(RN=CH)C6H4!n&' (n = 1, 2) frag$ent ee$ to "araegenera* the ret o'taine# %ith the %i#er in/etigate#,$ore fei'e 2-(Me2 NCH2)C6H4 gro"0 Ho%e/er, o$ei$"ortant #ifference reate# to the 'ine of the organic

gro" attache# to nitrogen %ere o'er/e# (i) roo$te$"eratre NMR "ectra in CC3 e/i#ence e+i/aence ofthe organic gro" at anti$on* for [2-(2′,4′,6′-Me3C6H2 N=CH)C6H4!2&'Br ($), %hie for [2-(2′,6′-ir 2C6H3 N=CH)C6H4!2&'Br () the NMR #ata in#icate not thenon-e+i/aence of the organic igan# (a %a ao o'er/e#in the oi# tate), 't ao the retriction of the free rotationof one of the '* 2,6-ir 2C6H3 gro" aron# the CLN(=C)inge 'on#G (ii) the teric tre "re/ent the intra$oecarcoor#ination of 'oth N( sp2) to an anti$on* ato$ in the#incear fi#e [2-(2′,6′-ir 2C6H3 N=CH)C6H452&'!2& (:)G(iii) in the co$"e cyclo-[2-(2′,6′-ir 2C6H3 N=CH)C6H45&'&!2[8(C)9! (44) the 8(C)9

frag$ent i coor#inate# to the fr ato$ of the all -cis

io$er of the fi#e 45, %hie in the reate# cyclo-[2-(Me2 NCH2)C6H45&'&!2[8(C)9! the a$e $eta car'on* niti coor#inate# to the cis-&' C7‒ trans-&'LN io$er of theheteroc*cic fi#e0 Theoretica cacation re/ea that in thega "hae the energ* #ifference 'et%een the geo$etricaio$er of the #i$er aociation of 9 an# thoe 'et%een the

geo$etrica io$er of 45 are $a (Z Y7$o)0 Mot ie*,e/era io$er are "reent in otion an# the "acing force "a* an i$"ortant roe for the cr*ta iFation "roce0

?8perimental ,ection

@eneral procedures

Mtincear NMR "ectra (1H, 13C) %ere recor#e# at roo$te$"eratre on a Brer I/ance 3;; (4, 2, , :, , 45, 44) an#a Brer I/ance ::: 9;; ($, 6, 9, ;) intr$ent0 The 1Hche$ica hift are re"orte# in nit (""$) reati/e to therei#a "ea of the #eterate# o/ent (ref0 CC 3 1H ?026 ""$G M&-d # 1H 209; ""$)0 The 13C che$ica hift are

re"orte# in nit (""$) reati/e to the "ea of the o/ent(ref0 CC3 13C ??0; ""$G M&-d * 13C 3043 ""$)0 1H an#13C reonance %ere aigne# ing 2 NMR e"eri$ent(C&O, HMC an# HMBC)0 The NMR "ectra %ere "rocee# ing the +estReC an# +estReNo(a oft%are029

Ma "ectra %ere recor#e# %ith a >innigan MIT 2;; (D:)an# an I""ie# Bio*te$ (T*"e Mariner) (D&:7IC:-T>)intr$ent0 :nfrare# "ectra %ere recor#e# on a BioRa# >T&-169 "ectro$eter, ing ITR-:R a $etho#0 Meting "oint%ere $eare# %ith an Dectrother$a 2;; a""arat an# arenot correcte#0 De$enta ana*e %ere carrie# ot %ith aerin-D$er 24;; an# a CHN-Ina*ator T*"e >ahID1112 (Co0 Ther$o) intr$ent0 I $ani"ation %ere

carrie# ot n#er an inert at$o"here of argon ing &chentechni+e0 &o/ent %ere #rie# an# freh* #itie# n#erargon "rior to e0 &tarting $ateria ch a 2-(BrCH2)C6H4Br, 2′,4′,6′-Me3C6H2 NH2, 2′,6′- ir 2C6H3 NH2,&'C3, .Br, .H, Na2&H2 or 8(C)6 %ere o'taine# fro$I#rich or Merc, an# %ere e# a recei/e#0

,ynthesis of 2-(2!"!"6!-#e$C6H2N=CH)C6H/r (4) 2-Bro$o'enFa#eh*#e (390;; g, # = 1099 g7c$ 3, 2201 $U, ;01$o) an# 2,4,6-tri$eth*aniine (2909; g, # = ;0 63 g7c$3,2609 $U, ;01 $o) %ere #io/e# in toene (1;; $U) in aron# 'otto$ fa0 The reaction $itre %a heate# at reffor h ing a ean-&tar a""arat to re$o/e the %ater0

Then the reaction $itre %a cooe# to roo$ te$"eratrean# the o/ent %a re$o/e# ing a rotar* e/a"orator to gi/ea 'ro%n oi %hich oi#ifie# at ; PC0 Thi oi# %arecr*taiFe# fro$ heane to gi/e the tite co$"on# a a*eo% $ateria (40; g, 9J), $" 91-92 PC0 Ina0 Cac#0 forC16H16BrN (3;2021) C, 6309G H, 9034G N 4063G >on# C,63026G H, 9016G N 4026J0 1H NMR (3;; MHF, CC3) δ 2016(6 H, , H-?′, CH3), 203; (3 H, , H-′, CH 3), 602 (2 H, , H-3′, C6H3), ?034 (1 H, ###, H-9, C 6H4, 3 HH = ?04, 4 HH = 10HF), ?044 (1 H, ##, H-4, C6H4, 3 HH = ?03 HF), ?063 (1 H, ##,H-6, C6H4, 3 HH = 0;, 4 HH = 102 HF), 02? (1 H, ##, H-3,C6H4, 3 HH = ?0?, 4 HH = 10 HF), 062 (1 H, , H-?, C =N)0 13C

This journal is © The Royal ocie!y o" Che#is!ry $year% Journal Name& $year%& [vol& ''('' | (

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NMR (?909 MHF, CC 3) δ 103; (, C-?′, CH 3), 2;0?3 (, C-′, CH3), 12906? (, C-2), 12?0;1 (, C-2′), 12?0?1 (, C-4),12063 (, C-3), 120? (, C-3′), 132032 (, C-9), 133012 (,C-6), 133033 (, C-4′), 13406 (, C-1), 14042 (, C-1′),162016 (, C-?, C H=N)0 M& (D:, ?; e\, 2;; PC), m$ (J) 3;1(?;) [M!, 222 (2;) [M - Br!, 146 (1;;) [M - C6H9Br!0 :R/(CH=N) 162 (/) c$] 10

,ynthesis of 2-(2!"6!-i%r2C6H$N=CH)C6H/r (2)

Co$"on# 2 %a "re"are# a #ecri'e# a'o/e for 4 fro$ 2- 'ro$o'enFa#eh*#e (2?0;; g, # = 1099 g7c$3, 1?0; $U, ;019$o) an# 2,6-#iio"ro"*aniine (2903 g, # = ;04 g7c$ 3, 2?09$U, ;019 $o), in toene (1;; $U)0 Ifter re$o/a of theo/ent ing a rotar* e/a"orator the re$aining 'ro%n oioi#ifie# at ; PC0 Recr*taiFation fro$ heane ga/e 2 a a*eo% $ateria (3 g, ?6J), $" ?4-?6 PC0 1H NMR (3;;MHF, CC3) δ 1021 (12 H, #, H-′, CH 3, 3 HH 60 HF), 20(2 H, he"t, H-?′, CH, 3 HH 60 HF), ?016 (3 H, $, H-3′,4′,C6H3), ?03? (1 H, ###, H-9, C 6H4, 3 HH = ?0?, 4 HH = 104 HF),?046 (1 H, ##, H-4, C 6H4, 3 HH = ?09 HF), ?069 (1 H, #, H-6,

C6H4, 3 HH = ?0? HF), 02? (1 H, ##, H-3, C6H4, 3 HH = ?0?, 4 HH

= 103 HF), 09 (1 H, , H-?, C =N)0 13C NMR (?909 MHF,CC3) δ 23099 (, C-′, CH3), 2?04 (, C-?′, CH), 1230;? (,C-3′), 12403 (, C-4′), 1290?3 (, C-1), 12?0? (, C-4),1202 (, C-3), 132043 (, C-9), 133021 (, C-6), 13409? (, C-2), 13?09 (, C-2′), 140; (, C-1′), 16104 (, C-?, C H=N)0M& (D:, ?; e\, 2;; PC), m$ (J) 343 (1;;) [M!, 32 (9)[M - CH3!, 1 (3;) [M - C6H9Br!0 :R /(CH=N) 1624 (/)c$] 10

,ynthesis of A2-(2!"!"6!-#e$C6H2N=CH)C6HB2,'/r ($)

I otion of 4 (20;; g, 6062 $$o) in TH> (?; $U) %aa##e# #ro"%ie, n#er tirring, to $agnei$ fiing (;01? g,

?0; $$o, ?J ece) acti/ate# %ith 1,2-#i'ro$oethane (;09$U)0 The a##ition %a co$"ete# after ;09 h an# the 'ro%nreaction $itre %a tirre# for frther 109 h n#er ref0Then it %a cooe# to roo$ te$"eratre an# the nreacte# Mg%a e"arate#0 The Krignar# otion %a a##e# #ro"%ie to aotion of &'C3 (;0?9 g, 303; $$o) in TH> (2; $U) at L?PC an# the reaction $itre %a tirre# at thi te$"eratre for1 h, then for 12 h at roo$ te$"eratre0 The o/ent %are$o/e# n#er /ac$ an# the oi* rei#e %a %ahe# %ith#ieth* ether an# heane, reting in an *eo% oi# %hich%a fitere# off an# #rie# n#er /ac$ (;0; g, 3J), $"24-291 PC0 Ina0 Cac#0 for C32H32BrN2&' (64602?) C,904?G H, 40G N 4033G >on# C, 9013G H, 901;G N 401?J0 1H

NMR (9;; MHF, CC3) δ 1069 (12 H, , H-?′, CH3), 202; (6H, , H-′, CH3), 60?; (4 H, , H-3′, C6H3), ?02; (2 H, ###, H-4, C6H4, 3 HH = ?04, 4 HH = ;0 HF), ?039 (2 H, #, H-3, C 6H4,3 HH = ?03 HF), ?04; (2 H, ###, H-9, C 6H4, 3 HH = ?09, 4 HH =;0 HF), ?06 (2 H, #, H-6, C6H4, 3 HH = ?04 HF), 02 (2 H, ,H-?, C =N)0 13C NMR (1290 MHF, CC3) δ 1?0?9 (, C-?′,CH3), 2;063 (, C-′, CH 3), 12?04; (, C-2′), 12?069 (, C-9),12024 (, C-3′), 13;0?; (, C-4), 131093 (, C-6), 13204 (,C-4′), 13029 (, C-3), 14;0? (, C-1), 14?0? (, C-1′),14049 (, C-2), 164034 (, C-?, C =N)0 M& (D&:), m$ (J)969 (1;;) [R 2&'! [R = 2-(2′,4′,6′-Me3C6H2 N=CH)C6H4!0 :R/(CH=N) 1624 (/) c$] 10

,ynthesis of A2-(2!"6!-i%r2C6H$N=CH)C6HB2,'/r () Iotion of 2 (20;; g, 901 $$o) in TH> (?; $U) %a a##e##ro"%ie #ring ;09 h, n#er tirring, to $agnei$ fiing(;019 g, 6029 $$o, ?09J ece), acti/ate# %ith 1,2-#i'ro$oethane (;09 $U)0 The 'ro%n reaction $itre %atirre# for a##itiona 109 h n#er ref, then cooe# to roo$te$"eratre an# the nreacte# Mg %a e"arate#0 The

Krignar# otion %a a##e# #ro"%ie to a otion of &'C 3

(;064 g, 20 $$o) in TH> (2; $U), at L? PC, an# thereaction $itre %a tirre# at thi te$"eratre for 1 h, thenfor 12 h at roo$ te$"eratre0 The o/ent %a re$o/e# n#er/ac$ an# the oi* rei#e %a %ahe# %ith heane an#ethano nti a *eo% "reci"itate #e"oite#0 The oi# %afitere# off, #rie# n#er /ac$, then #io/e# in CH 2C2 (4;$U) an# the otion %a treate# %ith an a+eo otion of.Br (;09 g, 406 $$o) at roo$ te$"eratre0 The reaction$itre %a tirre# for 12 h0 The organic a*er %a e"arate#,the a+eo a*er %a %ahe# %ith CH 2C2 (3 1; $U) an#the nifie# organic "hae %ere #rie# o/er Mg&40D/a"oration of the otion n#er /ac$ *ie#e# a a

*eo% oi# (;0; g, 43J), $" 229-226 PC0 Ina0 Cac#0 forC3H44BrN2&' (?3;043) C, 6204G H, 60;?G N 304G >on# C,6203;G H, 60;?G N 30?6J0 1H NMR (3;; MHF, CC3) δ ;046[3 H, #, H-′a1, CH3 (I), 3 HH 609 HF!, ;0? [3 H, #, H-′ a2,CH3 (I), 3 HH 609 HF!, ;09 [6 H, #, H-′1, CH3 (B), 3 HH 609HF!, 10;6 [12 H, $, H-′ '1 (I) H-′ '2 (I) H-′2 (B), CH3!,101 [1 H, he"t, H-?′a, CH (I), 3 HH 609 HF!, 209 [3 H, $, H-?′ ' (I) H-?′ (B), CH!, ?0;2-?03; [ H, $, H-9,6, C6H4 (B) H-3′a,3′ ',4′ (I) H-3′,4′ (B), C6H3!, ?049 [1 H, ##, H-4, C 6H4

(B), 3 HH = 602 HF!, ?09 [1 H, #, H-3, C 6H4 (B), 3 HH = ?02HF!, ?0?1 [1 H, ##, H-4, C 6H4 (I), 3 HH = ?01 HF!, ?0; [1 H,##, H-9, C6H4 (I), 3 HH = ?01 HF!, ?0? [1 H, #, H-3, C 6H4 (I),3 HH = ?0; HF!, 036 [1 H, , H-?, CH=N (B)!, 043 [1 H, , H-

?, CH=N (I)!, 0 [1 H, #, H-6, C6H4 (I), 3 HH = ?0; HF!0 13C NMR (?909 MHF, CC3) δ 220; [, C-′a1, CH3 (I)!, 230?[, H-′ '1 (I) H-′1 (B), CH3!, 2409 [, H-′2, CH3 (B)!,240; [, C-′ '2, CH3 (I)!, 290; [, C-′a2, CH 3 (I)!, 2?0?? [,C-?′, CH (B)!, 20;; [, C-?′a, CH (I)!, 204 [, C-?′ ', CH(I)!, 1220 [, C-3′ (B)!, 123023 [, C-3′a (I)!, 12306 [, C-3′ ' (I)!, 124029 [, C-4′ (B)!, 1260 [, C-4′ (I)!, 12022 [,C-4 (I)!, 12091 [, C-4 (B)!, 13102 [, C-9 (B)!, 13202 [,C-3 (I)!, 13301 [, C-3 (B)!, 133043 [, C-9 (I)!, 139099 [,C-6 (B)!, 13093 [, C-2′ (B)!, 1306 [, C-2,6 C-2′ ' (I)!,14;042 [, C-2′a (I)!, 143064 [, C-1′ (I)!, 14909 [, C-1 (B)!,14026 [, C-2, C-1′ (B)!, 19302 [, C-1 (I)!, 1640? [, C-?,CH=N (B)!, 16066 [, C-?, CH=N (I)!0 M& (D&:), m$ (J)

; (4;) [R 2&'Br 2! , 64 (1;;) [R 2&'! [R = 2-(2′,6′-ir 2C6H3 N=CH)C6H4!0 :R /(CH=N) 1634 ($) c$] 10

,ynthesis of A2-(2!"6!-i%r2C6H$N=CH)C6HD2,'B2, (:) Iotion of Na2&H2 (;0;4 g, ;016 $$o, ?;J ece) in%ater (1; $U) %a a##e# to a otion of (;019 g, ;021$$o) in toene (3; $U)0 The reaction $itre %a tirre#for 2 #a* at roo$ te$"eratre, then the *eo% organic "hae%a e"arate# an# the %ater otion %a %ahe# %ith CH 2C2

(2 ^ 3; $U)0 The nifie# organic "hae %ere #rie# o/eranh*#ro Na2&40 Re$o/a of the o/ent n#er /ac$ga/e : a a *eo% oi# (;012 g, 6J), $" 24?-24 PC0 Ina0

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Cac#0 for C?6H N4&&'2 (1333012) C, 604?G H, 6069G N 402;G>on# C, 602G H, 6062G N 402;J0 1H NMR (3;; MHF,CC3) δ ;03 (4 H, ,'r, H-′, CH 3), 209 ( H, ,'r, H-?′,CH), 60?3 (4 H, ,'r, H-4, C 6H4), ?0;6 (12 H, $, H-3′,4′,C6H3), ?024 ( H, $, H-3,9, C6H4), ?062 (4 H, #, H-6, C6H4,3 HH = ?02 HF), 034 (4 H, ,'r, H-?, CH=N)0 13C NMR (?909MHF, CC3) δ 230?2, 2401; (, C-′, CH3), 2?0?9 (, C-?′,

CH), 12203 (, C-3′), 124049 (, C-4′), 12016 (, C-3,9),131022 (, C-6), 13104 (, C-4), 13?033 (, C-2), 13069 (, C-2′), 13014 (, C-1), 1460?6 (, C-1′), 16406 (, C-?, CH=N)0M& (D&:), m$ (J) 132 (4) [M X H!, 64 (1;;) [R 2&'! [R= 2-(2′,6′-ir 2C6H3 N=CH)C6H4!0 :R /(CH=N) 1626 ($) c$] 10

,ynthesis of A2-(2!"!"6!-#e$C6H2N=CH)C6HB,'/r2 (6)

I otion of 4 (20;; g, 6062 $$o) in TH> (; $U) %aa##e# #ro"%ie, n#er tirring, to $agnei$ fiing (;01?9 g,?02 $$o, 1;J ece), acti/ate# %ith 1,2-#i'ro$oethane(;09 $U)0 The a##ition %a co$"ete# after ;09 h an# the 'ro%n reaction $itre %a tirre# for frther 2 h n#erref0 Then it %a cooe# to roo$ te$"eratre an# the

nreacte# Mg %a e"arate#0 The Krignar# otion %aa##e# #ro"%ie to a otion of &'C3 (1091 g, 6062 $$o) inTH> (2; $U), at L? PC, an# the reaction $itre %a tirre#at thi te$"eratre for 1 h, then for 12 h at roo$ te$"eratre0The o/ent %a re$o/e# n#er /ac$ an# the oi* rei#e%a %ahe# %ith heane an# ethano, %hen a *eo% oi##e"oite#0 The oi# %a fitere# off, #rie# n#er /ac$,then #io/e# in CH2C2 (4; $U) an# the otion %a treate#%ith an a+eo otion of .Br (10 g, 190 $$o) at roo$te$"eratre0 The reaction $itre %a tirre# for 12 h0 Theorganic a*er %a e"arate#, the a+eo a*er %a %ahe#%ith CH2C2 (3 1; $U) an# the nifie# organic "hae %a#rie# o/er Mg&40 D/a"oration of the otion n#er /ac$

*ie#e# 6 a a *eo% oi# (1022 g, 3?J), $" 22-23; PC0Ina0 Cac#0 for C16H16Br 2 N&' (9;30?) C, 3014G H, 302;G N20?G >on# C, 3094G H, 3069G N 204J0 1H NMR (9;; MHF,CC3) δ 2024 (6 H, , H-?′, CH3), 2032 (3 H, , H-′, CH3),606 (2 H, , H-3′, C6H3), ?06 (1 H, ###, H-4, C 6H4, 3 HH =?09, 4 HH = 102 HF), ?0; (1 H, ###, H-9, C6H4, 3 HH = ?06, 4 HH

= 103 HF), ?01 (1 H, ##, H-3, C6H4, 3 HH = ?09, 4 HH = 103 HF),094 (1 H, , H-?, C =N), 04 (1 H, #, H-6, C6H4, 3 HH = ?0HF)0 13C NMR (1290 MHF, CC3) δ 106 (, C-?′, CH3),2;01 (, C-′, CH3), 12033 (, C-1), 12096 (, C-3′, C-2′),131014 (, C-4), 13206 (, C-3), 13401; (, C-9), 136091 (, C-6), 13604 (, C-4′), 1306 (, C-2), 142014 (, C-1′), 160;(, C-?, C =N)0 M& (D&:), m$ (J) 424 (1;;) [R&'Br ! [R

= 2-(2′,4′,6′-Me3C6H2 N=CH)C6H4!0 : R /(CH=N) 161? ()c$] 10

,ynthesis of A2-(2!"6!- i%r2C6H$N=CH)C6HB,'/r2 (9) Iotion of 2 (30;; g, 0?1 $$o) in TH> (?; $U) %a a##e##ro"%ie, n#er tirring, to $agnei$ fiing (;029 g, 1;0;4$$o, 19J ece), acti/ate# %ith 1,2-#i'ro$oethane (;09$U)0 The a##ition %a co$"ete# after ;09 h, the 'ro%nreaction $itre %a tirre# for a##itiona 2 h n#er ref,then cooe# to roo$ te$"eratre an# the nreacte# Mg %ae"arate#0 The Krignar# otion %a a##e# #ro"%ie to aotion of &'C3 (10 g, 0?2 $$o) in TH> (2; $U), at L?

PC, an# the reaction $itre %a tirre# at thi te$"eratre for1 h, then for 12 h at roo$ te$"eratre0 The o/ent %are$o/e# n#er /ac$ an# the oi* rei#e %a %ahe# %ithheane, %hen a *eo% "reci"itate #e"oite#0 The oi# %afitere# off, #rie# n#er /ac$, then #io/e# in CH 2C2 (4;$U) an# the otion %a treate# %ith an a+eo otion of.Br (103; g, 1;02 $$o) at roo$ te$"eratre0 The reaction

$itre %a tirre# for 12 h0 The organic a*er %a e"arate#,the a+eo a*er %a %ahe# %ith CH 2C2 (3 1; $U) an#the nifie# organic "hae %ere #rie# o/er Mg&40D/a"oration of the otion n#er /ac$ affor#e# 9 a a*eo% oi# (209; g, 93J), $" 234-23? PC0 Ina0 Cac#0 forC1H422Br 2 N&' (94909) C, 410;G H, 40;6G N 209?G >on# C,4101G H, 309G N 209;J0 1H NMR (9;; MHF, CC3) δ 1016(6 H, #, H-′1, CH3, 3 HH 60 HF), 102 (6 H, #, H-′ 2, CH3, 3 HH

60? HF), 20 (2 H, he"t, H-?′, CH, 3 HH 60 HF), ?02 (3 H, $,H-3′,4′, C6H3), ?0?; (1 H, ##, H-4, C6H4, 3 HH = ?09 HF), ?01(2 H, $, H-3,9, C6H4), 04 (1 H, , H-?, CH=N), 0; (1 H, #,H-6, C6H4, 3 HH = 60? HF)0 13C NMR (1290 MHF, CC3) δ

2303 (, C-′2, CH3), 29063 (, C-′1, CH3), 204 (, C-?′,

CH), 12401 (, C-3′), 12?041 (, C-4′), 131016 (, C-4),13202 (, C-3), 13402; (, C-9), 13?03 (, C-6), 13049 (, C-2), 14;09 (, C-2′), 141042 (, C-1′), 1403 (, C-1), 16019(, C-?, CH=N)0 M& (D&:), m$ (J) 466 (1;;) [R&'Br ! [R= 2-(2′,6′-ir 2C6H3 N=CH)C6H4!0 :R /(CH=N) 1621 () c$] 10

,ynthesis of cyclo-A2-(2!"6!- i%r2C6H$N=CH)C6HD,'OB$

(;) I otion of .H (;0;22 g, ;03 $$o, 1;J ece) in%ater (1; $U) %a a##e# to a otion of 9 (;01; g, ;01$$o) in toene (2; $U)0 The reaction $itre %a tirre#for 4 #a* at roo$ te$"eratre, then the organic a*er %ae"arate# an# the a+eo "hae %a %ahe# %ith toene (2 19 $U)0 The toene otion %a #rie# o/er Mg&4, then

fitere# an# the o/ent %a re$o/e# n#er /ac$0 Therete# "ae *eo% ca* %a tritrate# %ith heane to affor#; a a coore oi# (;0;6 g, 3J), $" 14-19 PC0 Ina0Cac#0 for C9?H66 N33&'3 (12;6042) C, 960?9G H, 9091G N304G >on# C, 96034G H, 909;G N 3039J0 1H NMR (9;; MHF,CC3) δ 10; (36 H, $, H-′, CH3, cis trans), 3014 (6 H,$, H-?′, CH, cis trans), ?0;4 (2 H, ###, H-9, C6H4, cis, 3 HH

= ?04, 4 HH = 10; HF), ?01 (6 H, $, H-3′,4′, C 6H3, cis), ?024 (3H, $, H-3′,4′, C6H3, trans), ?03 [4 H, $, (H-4, C6H4, cis) (H-4,9, C6H4, trans)!, ?09? (1 H, ##, H-3, C6H4, trans, 3 HH =?02, 4 HH = 101 HF), ?06; (2 H, #, H-3, C 6H4, cis, 3 HH = ?02HF), 01 (2 H, #, H-6, C 6H4, cis, 3 HH = ?02 HF), 039 (2 H, ,H-?, C =N, cis), 036 (1 H, , H-?, C =N, trans), 09; (1 H,

##, H-6, C6H4, trans, 3 HH = ?0;, 4 HH = 104 HF)0 13C NMR(1290 MHF, CC3) δ 24033 (,'r, C-′, CH3, cis trans),2?0; (, C-?′, CH, cis), 20;2 (, C-?′, CH, trans), 123029 (,C-3′, cis) , 123043 (, C-3′, trans), 129011 (, C-4′, trans),129016 (, C-4′, cis), 1203 (, C-4, cis), 120 (, C-4,trans), 131062 (, C-9, cis), 13102 (, C-3, cis), 13106 (, C-9, trans), 1320; (, C-3, trans), 13309 (, C-6, cis), 13306(, C-6, trans), 13036 (, C-2, trans), 1309; (, C-2′, cis),13096 (, C-2′, trans), 1309 (, C-2, cis), 146049 (, C-1′,cis), 1460 (, C-1′, trans), 19022 (, C-1, trans), 190? (,C-1, cis), 166024 (, C-?, CH=N, cis), 166032 (, C-?, CH=N,trans)0 M& (D&:), m$ (J) 12;6 (9;) [M H!, ;9 (1;;)


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[(R&')2 H!, 4;2 (4) [R&' H! [R = 2-(2′,6′-

ir 2C6H3 N=CH)C6H4!0 :R /(CH=N) 162 (/) c$] 10

,ynthesis of cyclo-A2-(2!"!"6!-

#e$C6H2N=CH)C6HD,',B2 () I otion of Na2&H2(;0;6 g, ;026 $$o) in %ater (1; $U) %a a##e# to a otionof 6 (;013 g, ;026 $$o) in toene (19 $U)0 The reaction

$itre %a tirre# for 2 h at roo$ te$"eratre, then the*eo% organic "hae %a e"arate# an# the a+eo "hae%a %ahe# %ith toene (2 19 $U)0 The toene otion%a #rie# o/er anh*#ro Na2&40 D/a"oration of the otionn#er /ac$ affor#e# a a *eo% oi# (;0;? g, ?2J), $"23-24; PC0 Ina0 Cac#0 for C32H32 N2&2&'2 (?92024) C,910;G H, 402G N 30?2G >on# C, 9101?G H, 4043G N 3091J0 1H NMR (3;; MHF, CC3) δ 2013 (12 H, , H-?′, CH 3, io$era), 201 (12 H, , H-?′, CH3, io$er '), 202 (12 H, , H-′,CH3, io$er a'), 60? ( H, , H-3′, C 6H3, a'), ?031(2 H, ##, H-9, C6H4, 3 HH = ?02 HF, '), ?041 (2 H, ##, H-4,C6H4, 3 HH = ?03 HF, '), ?09 (2 H, ##, H-4, C 6H4, 3 HH = ?04HF, a), ?063 (2 H, #, H-3, C 6H4, 3 HH = ?04 HF, '), ?0?3 (4

H, $, H-3,9, C6H4, a), 0346 (2 H, , H-?, C =N, '), 0393(2 H, , H-?, C =N, a), 094 (2 H, #, H-6, C6H4, 3 HH = ?02HF, '), 012 (2 H, #, H-6, C6H4, 3 HH = ?09 HF, a)G integraratio 1041 for io$er a'0 13C NMR (?909 MHF, CC3) δ

1?0; (, C-?′, CH3, io$er a), 102 (, C-?′, CH3, io$er'), 2;0?4 (, C-′, CH3, io$er a'), 12049 (, C-4, '),1204 (, C-2′, '), 12096 (, C-3′, '), 1202 (, C-3′, a),120 (, C-2′, a), 120;? (, C-4, a), 131012 (, C-9, '),13201 (, C-3, '), 132024, 13206 (, C-37C-9, a), 134063(, C-4′, a), 1340?; (, C-4′, '), 1360;1 (, C-6, a), 136046(, C-6, '), 130?; (, C-2, '), 130; (, C-2, a), 1440(, C-1′, '), 149032 (, C-1′, a), 19204 (, C-1, '), 19303(, C-1, a), 16?0;1 (, C-?, C =N, '), 16?032 (, C-?,

C =N, a)0 M& (D:, ?; e\, 2;; PC), m$ (J) ?92 (?;) [M!,3?6 (6) [R&'&!, 343 (1;;) [R&'! [R = 2-(2′,4′,6′-Me3C6H2 N=CH)C6H4!0 :R /(CH=N) 1622 (/) c$] 10

,ynthesis of cyclo-A2-(2!"6!- i%r2C6H$N=CH)C6HD,',B2

(45) I otion of Na2&H2 (;0;6 g, ;026 $$o) in %ater(1; $U) %a a##e# to a otion of 9 (;01; g, ;01 $$o) intoene (3; $U)0 The reaction $itre %a tirre# for 2 h atroo$ te$"eratre, then the *eo% organic "hae %ae"arate# an# the a+eo "hae %a %ahe# %ith toene (2 3; $U)0 The toene otion %a #rie# o/er anh*#ro Na2&40 Re$o/a of the o/ent n#er /ac$ ga/e 45 a anorange oi# (;0;6 g, ;J), $" 2?6-2? PC0 Ina0 Cac#0 for

C3H44 N2&2&'2 (3604;) C, 9409?G H, 903;G N 3039G >on# C,940G H, 904G N 30?J0 1H NMR (3;; MHF, CC3) δ 101?(4 H, ,'r, H-′, CH3, io$er 45a45'), 30;6 ( H, $, H-?′,CH, 45a45'), ?022 (12 H, $, H-3′,4′, C6H3, 45a45'G 2H, $,H-9, C6H4, 45') ?042 (2 H, ##, H-4, C 6H4, 3 HH = ?03 HF,45'), ?06; (2 H, ##, H-4, C6H4, 3 HH = ?03 HF, 45a), ?0?2 (4 H,$, H-3,9, C6H4, 45aG 2 H, $, H-3, C6H4, 45'), 039 (4 H, $,H-?, CH=N, 45a45'G 2 H, $, H-6, C6H4, 45'), 0; (2 H, #,H-6, C6H4, 3 HH = ?02 HF, 45a)G integra ratio 101 for io$er45a45'0 13C NMR (?909 MHF, CC3) δ 230;, 2903; (,'r,C-′, CH3, io$er 45a45'), 2026 (, C-?′, CH, 45a), 202(, C-?′, CH, 45'), 12309, 123,64, 1290 (, C-3′,4′,

45a45'G C-9, 45'), 1204; (, C-4, 45'), 12019 (, C-4,45a), 132039 (, C-3, 45'), 13204, 1320? (, C-3,9, 45a),13906 (, C-6, 45a), 13603 (, C-6, 45'), 13094 (, C-2,45'), 130? (, C-2, 45a), 130?4 (, C-1′, 45a45'), 130(, C-2′, 45a45'), 1440?1 (, C-1, 45'), 1930?? (, C-1, 45a),166049 (, C-?, CH=N, 45'), 1660?4 (, C-?, CH=N, 45a)0 M&(D&:), m$ (J) 3? (1;;) [M H! [R = 2-(2′ ,6′ -

ir 2C6H3 N=CH)C6H4!0 :R /(CH=N) 161 () c$] 10

,ynthesis of cyclo-A2-(2!"6!-i%r2C6H$N=CH)C6HD,',B2AE(CO):B (44) I otion of[8(C)9(thf)! ["re"are# fro$ 8(C)6 (;0; g, ;024 $$oe) '* i rra#iation %ith an _\ a$", in TH> (2;; $U)! %a a##e#to 45 (;02; g, ;024 $$oe) in TH> (1; $U) an# the $itre%a tirre# for 12 h at roo$ te$"eratre0 Ifter re$o/a of theo/ent n#er /ac$, the re$aining *eo%-'ro%n "ro#ct%a %ahe# %ith heane (39 $U) to gi/e 44 a an orange- 'ro%n oi# (;01 g, 69J), $" 2?-23 PC0 Ina0 Cac#0 forC43H44 N29&2&'28 (116;03;) C, 44091G H, 302G N 2041G>on# C, 440?4G H, 302G N 202J0 1H NMR (3;; MHF,

CC3) δ 102; (24 H, $,'r, H-′, CH 3), 204 (4 H, ,'r, H-?′,CH), ?01 (6 H, ,'r, H-3′,4′, C 6H3), ?04 (4 H, $,'r, H-4,9,C6H4), ?0?; (2 H, $,'r, H-3, C6H4), 03 (2 H, , H-?, CH=N),09? (2 H, $,'r, H-6, C6H4)0 13C NMR (?909 MHF, CC3) δ

23061, 240;?, 2901;, 2906 (,'r, C-′, CH3), 2026, 20(,'r, C-?′, CH), 1230 (,'r, C-3′), 126066 (, C-4′), 1209?(, C-4), 13204, 132063 (, C-3,9), 13609 (, C-6), 13046 (,C-2), 1304 (, C-2′), 14306 (, C-1′), 19303 (, C-1),160;3 (, C-?, CH=N), 1041 (, C -e+, 1 8C = 12?0? HF),2;;03; (, C -a)0 M& (D&:), m$ (J) 1134 (1;;) [M -C!, 1;? (3) [M - 3C!, ?4 (2) [M - R&'&!, 632 (33)[(R&'&)8(C)! [R = 2-(2′,6′-ir 2C6H3 N=CH)C6H4!0 :R/(C) 2;69 (), 1?4 (%), 114 (/), 16 (/)G /(CH=N)

161 ($) c$] 10

Crystal structures

&o% #iffion of n-heane into CH2C2 otion affor#e# theioation of inge cr*ta of (41 /7/) or :, 9, CH2C2 an#45 (31 /7/)0 Cr*ta of 44;029CH3H %ere i$iar* gro%ning a n-heane-CH2C2 $itre (31), %hich containe#$ethano (ta'iiFer "reent in the $eth*ene chori#e)0 &o%#iffion of n-heane at a$'ient te$"eratre into a CHC 3

otion (41 /7/) rete# in cr*ta of 6CHC30 The #etaiof the cr*ta trctre #eter$ination an# refine$ent are gi/enin Ta'e 4 an# 90 The cr*ta %ere $onte# on cr*ooo" ( ,CH2C2) or attache# %ith .r*to` oi to a ga fi'er (:,6CHC3, 9, 45, 44;029CH3H)0 >or an# CH2C2 #ata%ere coecte# at roo$ te$"eratre, %hie for :, 6CHC3, 9,45 an# 44;029CH3H the cr*ta %ere cooe# n#er anitrogen trea$ at o% te$"eratre0 ata %ere coecte# onBrer &MIRT ID< (, CH2C2) an# for# (T*"eKe$ini) (:, 6CHC3, 9, 45, 44;029CH3H) #iffracto$eter,ing gra"hite-$onochro$ate# Mo-. ra#iation ( 0 = ;0?1;?3S)0 The trctre %ere refine# %ith aniotro"ic ther$a "ara$eter0 The h*#rogen ato$ %ere refine# %ith a ri#ing$o#e an# a $ta iotro"ic ther$a "ara$eter0 >or trctreo/ing an# refine$ent the oft%are "acage &HDU<-? %ae#02? The #ra%ing %ere create# %ith the ia$on#

1" | Journal Name& $year%& [vol& ''('' This journal is © The Royal ocie!y o" Che#is!ry $year%

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