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Journal of Organometallic Chemistry

journal homepage: www.elsevier .com/locate/ jorganchem

Volume 747, 1 December 2013

Contents
of the Main Group Elements 1 Special issue on Organometallic Chemistry
Biosketch – Special issue on Organometallic Chemistry of the Main Group Elements 2

Reviews

Russell N. Grimes

J. Organomet. Chem. 747 (2013) 4

Synthesis and serendipity in boron chemis-try: A 50 year perspective

Elsevier B.V.http://dx.doi.org/10.1016/S0022-328X(13)00731-6

The graphical abstract illustrates oneexample of an unexpected finding cited inthe paper, i.e., the oxidative fusion of twoiron-bound carborane ligands to form tet-racarbon carborane products.

�
Bohumil Stíbr

Carbon insertion into borane clusters vianucleophilic addition reactions of boraneand carborane anions

New approaches to the synthesis of carbor-anes and heterocarboranes based on addi-tion reactions of highly nucleophilic boron-cluster anions to multiply bonded sub-strates are briefly overviewed.

B

C

B

B

B

B

B

B

C

H

H

C NRH

B

C

B

B

B

B

B

B

C

H

H

H

CN

R

B

C

B

B

B

B

B

B

C

C

R

B

C

B

B

B

B

B

B

C

C

R

-NH3

C-insert

Zhu Yinghuai, Narayan S. Hosmane


Carborane-based transition metal com-plexes and their catalytic applicationsfor olefin polymerization: Current andfuture perspectives

Polyhedral carborane clusters have beenwidely used as suitable ligands to constructvarious transition metal complexes. Thecomplexes demonstrate unique coordinat-ing models and interesting reactivity. Thismini-review summarizes the syntheses andcatalytic applications for olefin polymer-ization, and discusses the future perspec-tives in this area.

http://dx.doi.org/10.1016/S0022-328X(13)00731-6

www.sciencedirect.com/science/journal/0022328X

http://www.elsevier.com/locate/jorganchem

http://dx.doi.org/10.1016/S0022-328X(13)00731-6

Contentsiv

Oleg A. Filippov, Natalia V. Belkova,Lina M. Epstein, Elena S. Shubina


Chemistry of boron hydrides orchestratedby dihydrogen bonds

Review covers recent developments in thestudies of boron hydrides reactivity orches-trated by dihydrogen bonds, focusing ontheir role in such reactions as proton transferand H2 evolution, dimerization and hydro-genedeuterium exchange.

V. Prakash Reddy, Avinash Vadapalli,Ekkehard Sinn, Narayan Hosmane


N-Heterocyclic carbenes in organofluorinechemistry

N-heterocyclic carbenes (NHC) and theirtransition metal ion complexes catalyzea variety of organofluorinations, includingolefin metathesis, trifluoromethylations,Heck and Suzuki coupling, hydro-defluorinations, and enantioselective fluo-rinations. Synthesis of various NHC-metalion complexes and their applications in thesynthesis of organofluorine compounds iscomprehensively reviewed.

N N..

0.5 mol%O

H H

F3C OH

R RCF3TMS

Regular Papers

Brendan Gleeson, Patrick J. Carroll,Larry G. Sneddon


Functionalized ferratricarbadecaboranylcomplexes for potential anticancerapplications

A library of functionalized cyclopentadienylferratricarbadecaboranyl complexes withpotential anticancer activity was synthe-sized by the attachment of N-heterocyclicand/or solubilizing groups at the tricarba-decaboranyl or cyclopentadienyl ligands. ANational Cancer Institute 60 cell line screenfor anticancer activity identified the mostactive substitution patterns for the series.

I.S. Ignatyev, G.S. Samokhin, T.A. Kochina,V.V. Belyaeva, S.Ya. Khaikin, M. Montejo,J.J. López González, M.G. Voronkov


Vibrational spectra and electronic structureof germatranols (HO)4 � n Ge(OCH2CH2)nNR3 � n (R ¼ H; n ¼ 1e3) with transannularGe/N bonding

Equilibrium structures of germatranols(HO)4 � nGe(OCH2CH2)nNR3 � n (R ¼ H, Me;n ¼ 1e3) and their centrosymmetric dimersare reported and have been used to supportthe assignment of their firstly recorded IRspectra in solid phase.

Contents v

Dmitry A. Loginov, Zoya A. Starikova,Maddalena Corsini, Piero Zanello,Alexander R. Kudinov


(Cyclopentadienyl)metalladicarbollides 3-(h-C5R5)-3,1,2-MC2B9H11 (M ¼ Co, Rh, Ir):Synthesis, electrochemistry, and bonding

Complexes 3-Cp-3,1,2-MC2B9H11 (M ¼ Co,Rh, Ir) were obtained by reactions of Tl[Tl(h-7,8-C2B9H11)] with [CpMI2]2 or[CpM(MeCN)3]2þ. The results of structural,electrochemical and theoretical studies arealso discussed.

Jonathan Bould,Michael G.S. Londesborough,John D. Kennedy, Ramón Macías,Rudolph E.K. Winter, Ivana Císa�rová,Pavel Kubát, Kamil Lang


Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaboraneclusters

Reaction of [(PMe2Ph)4Pt2B10H10] with EtNCproduces [(EtNC)2(PMe2Ph)3Pt2B10H10]which contains terminal and bridging iso-nitrile groups. The bridging EtNC may beejected by UV irradiation or replaced by COand then by SO2. DFT calculation models theproducts well.

Zi-Jian Yao, Bin Xu, Xian-Kuan Huo,Guo-Xin Jin


Homonuclear half-sandwich iridium andrhodium complexes containingdichalcogenolato-functionalized o-carbor-anyl ligands

Dichalcogenolato-functionalized nido-car-borane ((NMe4)[7,8-(HS)2-7,8-C2B9H10])ligand was investigated for the formation ofreactive 16-electron Ir and Rh complexes andthe construction of metale metal bonds.

Xiao Tang, Zhaojin Wang, Yizhi Li,Hong Yan


Reactivity of the 16-electron CpCo half-sandwich complex containing a B(3,6)-disub-stituted o-carborane-1,2-dithiolate ligand

In methanol complex 1 reacts with alkynesto lead to product 2 and isomerizes to 3. Inthe presence of [N(n-Bu)4]Br in THF complex1 can be transformed to ionic square-planarcomplex 4 which shows notably differentelectrochemical properties in contrast toanalogous carborane-free complexes.

Contentsvi

YY
Dieter Wöhrle, Olga Tsaryova,Andrey Semioshkin, Detlef Gabel,Olga Suvorova

Synthesis and photochemical properties ofphthalocyanine zinc(II) complexes contain-ing o-carborane units

o- Carboranyl-substituted phthalocyaninezinc(II) complexes were synthesized. Thephotocatalytic activities, singlet oxygenquantum yields and the photooxidativestabilities were determined. The carboranylsubstituted phthalocyanines showimproved photocatalytic properties andsinglet oxygen quantum yields.

N

NN

N

N

N

N

NZn

XX

X X

Y Y

o

CHBH

X: Spacer

Y: -H or CH3

6
Jianlin Chen, Shaoling Chen,Zhiguo Liu, Hao Feng,Yaoming Xie, R. Bruce King

Methylborabenzene ligands in binucleariron carbonyl derivatives: High spin statesand ironeiron multiple bonding

The lowest energy (h -C5H5BCH3)2Fe2(CO)4structures are the singlet doubly bridged cis-and trans-(h6-C5H5BCH3)2-Fe2(CO)2(m-CO)2structures. The triplet triply bridged (h6-C5H5BCH3)2Fe2(m-CO)3 structure is the low-est energy tricarbonyl structure. An unsym-metrical quintet (h6-C5H5BCH3)Fe]Fe(CO)2(h6-C5H5BCH3) structure is predictedto be the lowest energy dicarbonyl structure.

Rakesh K. Sharma, G. Kedarnath,Nisha Kushwah, Manoj K. Pal,Amey Wadawale, B. Vishwanadh,Bhaskar Paul, Vimal K. Jain


Indium(III) (3-methyl-2-pyridyl)selenolate:Synthesis, structure and its utility as a singlesource precursor for the preparation ofIn2Se3 nanocrystals and a dual source pre-cursor with [Cu{SeC5H3(Me-3)N}]4 for thepreparation of CuInSe2

Treatment of InCl3 with NaSeC5H3(Me-3)Nafforded [In{SeC5H3(Me-3)N}3]. The centralindium atom acquires a distorted octahedralgeometry. Thermolysis of [In{SeC5H3(Me-3)N}3] in various coordinating solvents anddifferent reaction conditions yielded differ-ent morphologies of indium selenide. Ther-molysis of 1:1 mixture of [In{SeC5H3(Me-3)N}3] and [Cu{SeC5H3(Me-3)N}]4 in variouscoordinating solvents gave nanocrystals ofcopper indium selenide.

Pau Farràs, Clara Viñas, Francesc Teixidor


Preferential chlorination vertices in cobal-tabisdicarbollide anions. Substitution ratecorrelation with site charges computed bythe two atoms natural population analysismethod (2a-NPA)

The radical chlorination reaction in metal-lacarborane anions, whose origin is kinetic,has preferential chorination sites. Thesubstitution reaction rates have beenrationalised by considering 2a-NPA on thestarting metallacarborane, [3,3’-Co(1,2-C2B9H11)2]�, unperturbed by chlorine sub-stituents. The 2a-NPA value is defined asthe sum of the NPA charges of the twobonded atoms.

Contents vii

Alexander A. Maleev, Anatoly A. Fagin,Vasily A. Ilichev, Mikhail A. Lopatin,Alexey N. Konev, Maksim A. Samsonov,Georgy K. Fukin, Mikhail N. Bochkarev


Lanthanide pentafluorophenolates. Synthe-sis, structure and luminescent properties

The lanthanide pentafluorophenolatesLn(OC6F5)3, Ln(OC6F5)3(MeOH), Ln(OC6-F5)3(Et2O)3, Ln(OC6F5)3(MeOH)3, Ln(C6F5O)3(phen), Ln(OC6F5)3(phen)2(Et2O), Ln(OC6F5)3(phen)(Et2O)3, Ln(OC6F5)3(phen)2(H2O), Ln(OC6F5)3(phen)2(MeOH), Ln(OC6F5)3(py)5 and Ln(OC6F5)3(bpy)2 where Ln ¼ Ce, Nd, Sm, Eu, Gd,Tb, Dy, Ho, Er, Yb were prepared and fullycharacterized. Luminescence spectra of theobtained complexes contain the bands ofligand-centered and metal-centered emission.

Nanditha G. Nair, Jose L. Mendoza-Cortes,Ravinder Abrol, William A. Goddard, III ,V. Prakash Reddy


1,3-Sigmatropic fluorine migration to boronin McLafferty type of rearrangements:Observation of tetrafluorobenzyne radicalcation and trifluorobenzyne cation by CID-mass spectrometry

The 1,3-sigmatropic fluorine migrationleading to the McLafferty rearrangement oftris(pentafluorophenyl)boroxine 1 results inthe formation of the tetrafluorobenzyneradical cation 1c, whereas similar rear-rangement involving 1,3-hydrogen rear-rangement is not observed for thenonfluorinated analog, triphenylboroxine 2.The DFT calculations corroborate theseresults.

Bernd Wrackmeyer, Elena V. Klimkina,Wolfgang Milius


Oxidation of 1,3,2-diselenaphospholaneswith an annelated dicarba-closo-dodeca-borane(12) unit by addition of sulfur andselenium. Molecular structure of a novel1,2,4,5-tetraselena-3-phospha heterocycle

The insertion of selenium into PeSe bondswas observed to give novel seven-membered rings, containing two m-Se2units.

Anton P. Tyurin, Fedor M. Dolgushin,Alexander F. Smol’yakov, Ivan D. Grishin,Dmitrii I. D’yachihin, Elena S. Turmina,Dmitry F. Grishin, Igor T. Chizhevsky


Synthesis and characterization of mixed-ligand ferracarboranes. Direct metalationof the nido-carborane [nido-7,8-C2B9H12]�

mono-anion with 14-e [Ph2P(CH2)nPPh2]FeCl2 (n ¼ 2, 3)

Novel mononuclear mixed-ligand 17-e and18-e closo-ferracarboranes were synthe-sized and characterized by X-ray diffractionstudies. In addition, the paramagneticcomplexes were attempted to use as ATRPcatalyst precursors for MMA and styrene,however, with moderate success. The redoxchemistry of these complexes was alsostudied.

Contentsviii

Bohumír Gr}uner, Volker Böhmer,Crenguta Dordea, Pavel Selucký,Mária Bubeníková


Anionic tert-butyl-calix[4]arenes substitutedat the narrow and wide rim by cobaltbis(dicarbollide)(1�) ions andCMPO-groups.Effect of stereochemistry and ratios of thefunctional groups on the platform on theextraction efficiency for Ln(III)/An(III)

The series of ionic calix[4]arenes substitutedat the narrow/wide rim with an unpaired/paired number (n) of cobaltbis(dicarbollide)(1�) anions (1�) (n ¼ 1, 2and 3) and (4 � n) CMPO groups have beensynthesized. The influence of their sub-stitutions and stereochemistry on the effi-ciency for Ln(III)/An(III) group extraction isreported.

K.I. Tugashov, D.A. Gribanyov,F.M. Dolgushin, A.F. Smol’yakov,A.S. Peregudov, M.Kh. Minacheva,B.N. Strunin, I.A. Tikhonova, V.B. Shur


Coordination chemistry of mercury-containing anticrowns. Complexation of ni-trate and sulfate anions with the three-mercury anticrown (o-C6F4Hg)3and the influence of the nature of a coun-tercation on the structure ofthe resulting nitrate complexes

The paper reports the synthesis of double-decker sandwich complexes of the mercuryanticrown (o-C6F4Hg)3 with nitrate andsulfate anions. On the example of the nitratecomplexes, it has been shown that the na-ture of a countercation can exert an essentialinfluence upon the structure of anticrowncomplexes with anionic species.

Yong Nie, Jinling Miao, Hans Pritzkow,Hubert Wadepohl, Walter Siebert


Weak intramolecular CeH/HeB andCeH/Cl interactions in C-aminoboryl-o-carboranes

Three C-borylated o-carborane derivatives,which feature a combination of weakintramolecular hydrogenehydrogen andweak CeH/Cl hydrogenechlorine in-teractions, have been synthesized by thereactions of dilithio-o-carboraneLi2C2B10H10 with aminodichloroboranesR2NBCl2 (R ¼ Et, iPr) and structurallycharacterized.

David Sedlák, Barbara Eignerová,Martin Dra�cínský, Zbyn�ek Janou�sek,Petr Bart�un�ek, Martin Kotora


Synthesis and evaluation of 17a-(carbor-anylalkyl)estradiols as ligands for estrogenreceptors a and b

Cross metathesis offers a convenientapproach for synthesis of a series of 17a-(carboranylalkyl)estradiols that tested as li-gands for estrogen receptors.

Contents ix

Algin Oh Biying, Karen Tang Yuanting,Narayan S. Hosmane, Zhu Yinghuai


Synthesis of carboranyl amides catalyzed byrecyclable Pd (0) nanoparticles supportedon carbon nanotubes (CNTs)

Well-dispersed, MWCNTs-supported palla-dium nanoparticles with small size andnarrow size distribution were synthesized.The nanocomposite was found to be a highlyefficient and recyclable catalyst for theaminocarboranylation reaction of aryl hal-ide to form carboranyl amides. The catalystwas recyclable at least three times withsustained activity.

Hiroyuki Nakamura, Yuka Yasui,Hyun Seung Ban


Synthesis and biological evaluation of ortho-carborane containing benzoxazole as an in-hibitor of hypoxia inducible factor (HIF)-1transcriptional activity

ortho-Carborane containing benzoxazole 2bwhich has a carboxylic group on the ben-zoxazole ring, exhibited significant inhibitionof hypoxia-induced HIF-1 transcriptional ac-tivity with the IC50 value of 14.4 mM towardHeLa cell-based reporter gene assay.

Aleksandra Jankowiak,Junichiro Kanazawa,Piotr Kaszynski, Ryo Takita,Masanobu Uchiyama


[closo-1-CB11H11-1-Ph]� as a structural ele-ment for ionic liquid crystals

Ions pairs of anisometric anion, derived from[closo-1-CB11H11-1-Ph]�, and substitutedpyridinium cation exhibit a SmA phase.

Agnieszka B. Olejniczak, Ryszard Kierzek,Eric Wickstrom, Zbigniew J. Lesnikowski


Synthesis, physicochemical and biochemicalstudies of anti-IRS-1 oligonucleotides con-taining carborane and/or metallacarboranemodification

DNA-oligomers modified simultaneouslywith both, carborane and metallacarboraneboron clusters have been synthesized for thefirst time. The antisense activity of thesebioorganic-inorganic constructs and abilityto silence the insulin receptor substrate 1(IRS-1) gene overexpressed in several typesof tumors was tested in preliminary exper-iments.

Contentsx

�
Maria Tesa Serrate, David Ellis,Georgina M. Rosair, Alan J. Welch

Capping the thiaborate anion [7-nido-SB10H11]�

The anion [7-nido-SB10H11] is readilydeprotonated and then capitated witheither a {BH} fragment or a {MLn} fragment.

S

M

S S

H

�
René Frank, Henry Auer,Evamarie Hey-Hawkins

Functionalisation of the nido-dicarbaborateanion nido-7,8-C2B9He

12 by hydrideabstraction

Substitution at nido-7,8-C2B9H12 (1) leads tosymmetric products 10-R-nido-7,8-C2B9H11(R ¼ THF, THT, CH3CN, OH, Ph2S). Ph2S couldeasily be replaced by pyridine and triethyl-amine. Additionally, reactions of 1 withCF3SO3H in the presence of CH3CN orCH3SCN gave 9-CH3C(NH2)-nido-7,8-C2B9H11and 9-CH3SC(NH2)-nido-7,8-C2B9H11 byelectrophilic substitution.

Zaozao Qiu, Liang Deng, Zuowei Xie


Reaction of Li2C2B10Me8H2 with NiCl2.Ligand effects on stability of Ni-octame-thylcarboryne complexes

Phosphines play an important role in theformation of different kinds of products inthe reaction of 1,2-Li2-4,5,7,8,9,10,11,12-Me8-1,2-C2B10H2 with NiCl2(phosphine).

Teodora Popova, Adnana Zaulet,Francesc Teixidor,Radostina Alexandrova,Clara Viñas


Investigations on antimicrobial activity ofcobaltabisdicarbollides

Antimicrobial properties of the severalcobaltabisdicarbollides derivatives havebeen investigated.

Contents xi

Igor L. Fedushkin, Mikhail V. Moskalev,Evgenii V. Baranov, Gleb A. Abakumov


Addition of diphenylacetylene and methyl-vinylketone to aluminum complex of redox-active diimine ligand

Combination of aluminum with redox-active dpp-bian ligand allows formation ofmolecular system that reveals an unusualreactivity toward unsaturated organic mol-ecules, e.g. alkynes and conjugated enones.

D.V. Airapetyan, V.S. Petrosyan,S.V. Gruener, K.V. Zaitsev,D.E. Arkhipov, A.A. Korlyukov


Disproportionation reactions within the se-ries of coordinated monoorganostannanes

Interaction of monoorganotin trichlorideswith O-TMS-amides of 2-hydroxycarboxylicacids afforded a number of mononuclearand binuclear organotin complexes. It hasbeen shown that the coordination com-pounds of monoorganotin, depending onthe substituent at the tin atom, had thetendency for the disproportionation reac-tion, giving diorganostannanes and inor-ganic coordination compounds as itsproducts.

Pritam Shankhari, Dipak Kumar Roy,K. Geetharani, R.S. Anju,Babu Varghese, Sundargopal Ghosh


Synthesis and structural characterization ofgroup 5 dimetallaheteroboranes

Pyrolysis of an in situ generated intermedi-ate, obtained from the reaction of group 5metal polychlorides and [LiBH4$THF], inpresence of diphenyl diselenide or ditellur-ide yielded selenium rich compound,[(CpNb)2BH(Se)4] and divanadatellurabor-ane, [(CpV)2B3H9(m3-Te)] respectively.

Note

Igor B. Sivaev, Alexander V. Prikaznov,Sergey A. Anufriev


On relative electronic effects of polyhedralboron hydrides

Relative electron-donating properties ofanionic polyhedral boron hydrides were com-pared on basis of the analysis of the 1H NMRchemical shifts of the b-hydrogens in theirderivatives. The electron donating propertiesof boron clusterswere found to decrease in thefollowing order [2-B10H9]2� > [B12H11]2� w[12-CB11H11]� w [10-nido-7,8-C2B9H10]� > [8-3,30-Co(1,2-C2B9H10)(1,2-C2B9H11)]� > [1-B10H9]2�.

Contentsxii

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