supplementary information · 2010-04-23 · final r indices [i>2sigma(i)] r1 = 0.0593, wr2 =...

© 2010 Macmillan Publishers Limited. All rights reserved.

SUPPLEMENTARY INFORMATIONdoi: 10.1038/nchem.617

nature chemistry | www.nature.com/naturechemistry 1

1

Supporting Material

Isolation of Crystalline Carbene-Stabilized P2-Radical Cations and P2-Dication

Olivier Back,a Bruno Donnadieu,a Pattiyil Parameswaran,b Gernot Frenking,b

Guy Bertranda

aUCR-CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of

California Riverside, Riverside, CA 92521-0403

bFachbereich Chemie, Philipps-Universitat Marburg, Hans-Meerwein-Strasse,

35032 Marburg, Germany

E-mail: [email protected]


2 nature chemistry | www.nature.com/naturechemistry

SUPPLEMENTARY INFORMATION doi: 10.1038/nchem.617

2

Table S1. Crystal data and structure refinement for 2+.

. CCDC number: 752718

_____________________________________________________________________________________________

Empirical formula C46H70N2P2 , B(C6F5)4

Formula weight 1392.03

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P2(1)/c

Unit cell dimensions a = 13.2289(17) Å α= 90°

b = 23.185(3) Å β= 96.490(2)°

c = 23.482(3) Å γ = 90°

Volume 7156.1(16) Å3

Z 4

Density (calculated) 1.292 Mg/m3

Absorption coefficient 0.153 mm-1

F(000) 2876

Crystal size 0.28 x 0.16 x 0.10 mm3

Theta range for data collection 1.75 to 24.71°

Index ranges -15<=h<=15, -27<=k<=27, -27<=l<=25

Reflections collected 46006

Independent reflections 12185 [R(int) = 0.0914]

Completeness to theta = 24.71° 99.9 %

Absorption correction Sadabs

Max. and min. transmission 0.9848 and 0.9583

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 12185 / 0 / 869

Goodness-of-fit on F2 0.943

Final R indices [I>2sigma(I)] R1 = 0.0593, wR2 = 0.1165

R indices (all data) R1 = 0.1209, wR2 = 0.1364

Extinction coefficient 0.00009(8)

Largest diff. peak and hole 0.635 and -0.308 e.Å-3




3

Table S2. Crystal data and structure refinement for 4+.


_____________________________________________________________________________________________

Empirical formula C54H72N4P2 B(C6F5)4, C6H5F




Crystal system Monoclinic

Space group P2(1)/n

Unit cell dimensions a = 12.4547(11) Å α= 90°.

b = 39.760(4) Å β= 97.9780(10)°.

c = 16.5856(15) Å γ = 90°.

Volume 8133.8(13) Å3

Z 4



F(000) 3332



Index ranges -14<=h<=14, -45<=k<=46, -19<=l<=19











Extinction coefficient 0.00033(19)





4

Table S3. Crystal data and structure refinement for 4++


_____________________________________________________________________________________________

Empirical formula C28H36N2P, CF3SO3




Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 11.9641(8) Å α= 88.469(3)°

b = 12.3049(7) Å β= 62.462(3)°

c = 12.6616(7) Å γ = 63.204(3)°

Volume 1435.93(15) Å3

Z 2



F(000) 600



Index ranges -14<=h<=7, -15<=k<=12, -15<=l<=13















5

2. Computational details

118.3 195.1 [P2(CAAC)2] (2) [P2(CAAC)2]

+ (2+.) [P2(CAAC)2]2+ (2++)

De = 94.9 De = 218.4 De = 443.0

94.4 186.1 [P2(NHC)2] (4) [P2(NHC)2]

+ (4+.) [P2(NHC)2]2+ (4++)

De = 62.3 De = 209.6 De = 443.2

Figure S4: Optimized geometries (MO5-2X/def-SVP) of neutral and charged complexes of [P2(CAAC)2] and [P2(NHC)2]. Bond distances in Å, bond angles in deg and ionization energies in kcal/mol. D

e is the energy (kcal/mol) required to dissociate the molecules into (P2)

q (q = 0 - +2) and two carbene ligands.




6

Table S5: Calculated NBO Charge Distribution at MO5-2X/def-SVP.

2 2+. 2++

4 4+. 4++

P 0.096 0.183 0.380 -0.068 0.077 0.367

P' 0.102 0.183 0.353 -0.043 0.082 0.367

C∝ -0.061 0.087 0.198 0.133 0.228 0.209

C'∝ -0.068 0.087 0.187 0.126 0.193 0.209

NA -0.511 -0.409 -0.352 -0.470 -0.414 -0.388

NA' -0.467 -0.417 -0.388

NB -0.514 -0.409 -0.344 -0.473 -0.423 -0.388

NB' -0.472 -0.421 -0.388

Carbene 1 -0.092 0.317 0.642 0.061 0.450 0.633

Carbene 3 -0.105 0.317 0.625 0.051 0.391 0.633




7

Table S6: Calculated Atomic Spin Densities of Radical Cations at MO5-2X/def-SVP.

2+.

4+.

P 0.266 0.444

P' 0.266 0.326

C∝ 0.078 0.000

C'∝ 0.078 0.002

NA 0.141 0.025

NA' 0.025

NB 0.141 0.061

NB' 0.066

CAβ 0.004

CAβ' 0.006

CBβ 0.007

CBβ' 0.021




8

Total energies (in a.u.) and Cartesian coordinates (in Å, MO5-2X/def-SVP)

P2(CAAC)2(2) E = -2585.409420 P 1.033125000 0.423891000 0.069154000 N 3.378312000 -0.793993000 -0.323576000 C 2.021573000 -0.965703000 -0.228634000 C 1.706916000 -2.456760000 -0.407066000 C 1.025037000 -3.014963000 0.863101000 H 0.119418000 -2.437516000 1.076317000 H 1.701231000 -2.873735000 1.718906000 C 0.635222000 -4.484537000 0.706582000 H 1.533511000 -5.107765000 0.568375000 H 0.148716000 -4.830803000 1.628878000 C -0.297614000 -4.663356000 -0.490616000 H -0.596290000 -5.715560000 -0.593591000 H -1.215788000 -4.078121000 -0.322697000 C 0.381662000 -4.175558000 -1.769224000 H -0.297656000 -4.275278000 -2.626575000 H 1.251217000 -4.816723000 -1.983007000 C 0.814475000 -2.713240000 -1.642367000 H -0.084240000 -2.089266000 -1.558289000 H 1.341757000 -2.389686000 -2.549671000 C 3.110909000 -3.097741000 -0.555277000 H 3.406251000 -3.558160000 0.397435000 H 3.136732000 -3.880588000 -1.321920000 C 4.091821000 -1.964607000 -0.888728000 C 4.032436000 0.397901000 0.125858000 C 4.386756000 0.486536000 1.493402000 C 5.042033000 1.634927000 1.942081000 H 5.322955000 1.713547000 2.991604000 C 5.334493000 2.682360000 1.075150000 H 5.850404000 3.568873000 1.442169000 C 4.949291000 2.599860000 -0.255913000 H 5.155525000 3.432891000 -0.927371000 C 4.282686000 1.473303000 -0.751137000 C 4.279511000 -1.838742000 -2.405995000 H 3.324100000 -1.648705000 -2.908668000 H 4.699017000 -2.774113000 -2.799215000 H 4.971338000 -1.026533000 -2.649113000 C 5.458588000 -2.168839000 -0.242636000 H 6.114233000 -1.308347000 -0.429497000 H 5.926911000 -3.061193000 -0.677402000 H 5.372410000 -2.317081000 0.838430000 C 4.038005000 -0.595671000 2.503980000




9

H 3.660751000 -1.460194000 1.946734000 C 5.255175000 -1.042028000 3.323728000 H 6.102907000 -1.314899000 2.683061000 H 4.992210000 -1.909518000 3.943731000 H 5.590858000 -0.245740000 4.000790000 C 2.915126000 -0.124560000 3.438513000 H 2.631689000 -0.932832000 4.126778000 H 2.030992000 0.173775000 2.863658000 H 3.247184000 0.733742000 4.039172000 C 3.817495000 1.489853000 -2.197086000 H 3.289360000 0.549245000 -2.383761000 C 2.821243000 2.631016000 -2.441912000 H 1.984721000 2.564457000 -1.738312000 H 2.425496000 2.572867000 -3.464986000 H 3.303832000 3.610514000 -2.321730000 C 4.997400000 1.611232000 -3.170957000 H 5.461775000 2.603374000 -3.091683000 H 4.653250000 1.485999000 -4.206411000 H 5.778115000 0.867495000 -2.970289000 P -1.013813000 -0.384278000 0.197897000 N -3.396482000 0.801327000 0.326284000 C -2.039817000 1.002683000 0.286933000 C -1.771958000 2.512172000 0.324882000 C -1.045869000 2.948048000 -0.967598000 H -0.123940000 2.366732000 -1.075382000 H -1.679921000 2.699058000 -1.830942000 C -0.687642000 4.433790000 -0.956613000 H -1.602187000 5.047844000 -0.927278000 H -0.164694000 4.688732000 -1.888819000 C 0.184505000 4.762565000 0.254608000 H 0.458128000 5.826509000 0.256487000 H 1.120071000 4.184545000 0.191458000 C -0.542605000 4.396515000 1.547659000 H 0.094297000 4.605373000 2.417778000 H -1.434850000 5.033640000 1.652480000 C -0.937485000 2.918258000 1.559635000 H -0.023674000 2.310788000 1.576199000 H -1.493856000 2.677675000 2.475065000 C -3.197548000 3.121042000 0.350161000 H -3.466116000 3.470053000 -0.656574000 H -3.277588000 3.977867000 1.029190000 C -4.158444000 1.995281000 0.761040000 C -3.996423000 -0.437041000 -0.067568000 C -4.273076000 -0.631964000 -1.441874000 C -4.871558000 -1.828636000 -1.840718000 H -5.093067000 -1.989464000 -2.895105000 C -5.183264000 -2.820627000 -0.916701000




10

H -5.655415000 -3.745738000 -1.245462000 C -4.873394000 -2.633146000 0.423691000 H -5.093935000 -3.422228000 1.142038000 C -4.264302000 -1.454797000 0.870068000 C -4.384431000 2.001606000 2.278638000 H -3.438985000 1.873939000 2.818578000 H -4.829701000 2.959837000 2.577414000 H -5.068124000 1.200742000 2.576987000 C -5.511085000 2.096578000 0.063062000 H -6.144593000 1.235101000 0.311713000 H -6.019317000 3.008872000 0.400604000 H -5.398759000 2.146480000 -1.024930000 C -3.896745000 0.387825000 -2.505587000 H -3.601536000 1.308858000 -1.990997000 C -5.067077000 0.713805000 -3.441064000 H -5.969950000 0.992891000 -2.883467000 H -4.795779000 1.544883000 -4.105627000 H -5.318054000 -0.145377000 -4.076876000 C -2.686089000 -0.094737000 -3.316929000 H -2.399900000 0.663798000 -4.058664000 H -1.828680000 -0.284369000 -2.660401000 H -2.927479000 -1.022992000 -3.853497000 C -3.876135000 -1.351671000 2.334685000 H -3.370438000 -0.390305000 2.473246000 C -2.880184000 -2.453765000 2.720928000 H -2.005074000 -2.427642000 2.061812000 H -2.543043000 -2.310150000 3.756374000 H -3.343435000 -3.447412000 2.651868000 C -5.106177000 -1.415342000 3.249963000 H -5.555623000 -2.417246000 3.222275000 H -4.821241000 -1.205933000 4.289766000 H -5.881535000 -0.700089000 2.949227000 P2(CAAC)2

+(2+.) E = -2585.220905 P 0.951948000 0.395292000 0.242481000 N 3.301431000 -0.853282000 0.122999000 C 1.995711000 -1.065338000 0.193673000 C 1.705345000 -2.558730000 0.286690000 C 0.689079000 -2.917042000 1.387143000 H -0.255250000 -2.392314000 1.203769000 H 1.070010000 -2.571971000 2.359289000 C 0.395985000 -4.417482000 1.404463000 H 1.308651000 -4.986544000 1.639546000 H -0.323518000 -4.634681000 2.204395000 C -0.158666000 -4.863549000 0.051803000




11

H -0.383112000 -5.937737000 0.062664000 H -1.108026000 -4.336759000 -0.136969000 C 0.826845000 -4.542506000 -1.070861000 H 0.402548000 -4.815815000 -2.045753000 H 1.734144000 -5.151957000 -0.946357000 C 1.185141000 -3.054529000 -1.088697000 H 0.286605000 -2.480113000 -1.351548000 H 1.931864000 -2.847101000 -1.866843000 C 3.098972000 -3.136047000 0.630357000 H 3.160906000 -3.301045000 1.713976000 H 3.287405000 -4.096200000 0.139031000 C 4.147175000 -2.094771000 0.214618000 C 3.871493000 0.457639000 -0.101855000 C 4.238676000 1.253184000 1.005334000 C 4.829875000 2.493415000 0.747872000 H 5.130422000 3.121415000 1.585254000 C 5.024106000 2.946471000 -0.551024000 H 5.491933000 3.913891000 -0.727360000 C 4.597457000 2.173189000 -1.623701000 H 4.720346000 2.550987000 -2.637472000 C 4.004853000 0.922595000 -1.429451000 C 4.806660000 -2.412398000 -1.128034000 H 4.078447000 -2.627627000 -1.916246000 H 5.438208000 -3.299478000 -0.998065000 H 5.447950000 -1.583132000 -1.446754000 C 5.246927000 -1.941176000 1.260205000 H 5.939939000 -1.136228000 0.986235000 H 5.812646000 -2.880208000 1.301918000 H 4.838525000 -1.746601000 2.256462000 C 3.949301000 0.883536000 2.453731000 H 3.492964000 -0.113472000 2.470539000 C 5.218642000 0.863052000 3.316253000 H 6.001648000 0.224636000 2.893740000 H 4.980481000 0.500143000 4.324444000 H 5.631870000 1.874423000 3.420787000 C 2.935012000 1.862895000 3.065874000 H 2.675822000 1.544418000 4.083926000 H 2.016827000 1.910681000 2.469548000 H 3.360078000 2.873199000 3.127087000 C 3.484446000 0.177614000 -2.651504000 H 3.126708000 -0.804730000 -2.329678000 C 2.288072000 0.914599000 -3.271228000 H 1.464505000 1.010153000 -2.554749000 H 1.922261000 0.362255000 -4.146740000 H 2.578489000 1.920514000 -3.602504000 C 4.570022000 -0.028049000 -3.716242000 H 4.857077000 0.927241000 -4.173707000




12

H 4.188879000 -0.672728000 -4.518646000 H 5.476038000 -0.487309000 -3.305164000 P -0.951553000 -0.394870000 -0.241017000 N -3.301403000 0.853153000 -0.122262000 C -1.995725000 1.065576000 -0.192413000 C -1.705887000 2.559063000 -0.285963000 C -0.689284000 2.917396000 -1.386059000 H 0.255516000 2.394031000 -1.201243000 H -1.068940000 2.570866000 -2.358189000 C -0.398047000 4.418167000 -1.404560000 H -1.311404000 4.985839000 -1.640292000 H 0.321343000 4.635647000 -2.204520000 C 0.155774000 4.865971000 -0.052162000 H 0.378829000 5.940438000 -0.063796000 H 1.105818000 4.340593000 0.137110000 C -0.829390000 4.544432000 1.070685000 H -0.405233000 4.818618000 2.045390000 H -1.737317000 5.152920000 0.946075000 C -1.186329000 3.056109000 1.089257000 H -0.287289000 2.482682000 1.352417000 H -1.932928000 2.848365000 1.867457000 C -3.099557000 3.135715000 -0.630573000 H -3.160800000 3.300850000 -1.714223000 H -3.288910000 4.095687000 -0.139262000 C -4.147615000 2.094083000 -0.215525000 C -3.870921000 -0.458087000 0.101986000 C -4.236172000 -1.253602000 -1.005682000 C -4.827012000 -2.494217000 -0.749169000 H -5.126023000 -3.122276000 -1.587041000 C -5.022481000 -2.947682000 0.549430000 H -5.489806000 -3.915481000 0.725018000 C -4.597512000 -2.174345000 1.622757000 H -4.721323000 -2.552321000 2.636368000 C -4.005504000 -0.923360000 1.429369000 C -4.808644000 2.412039000 1.126269000 H -4.081268000 2.628111000 1.915092000 H -5.440575000 3.298701000 0.995253000 H -5.449827000 1.582644000 1.444790000 C -5.246121000 1.939011000 -1.262311000 H -5.938508000 1.133342000 -0.988895000 H -5.812865000 2.877379000 -1.304930000 H -4.836492000 1.744567000 -2.258112000 C -3.944677000 -0.883340000 -2.453417000 H -3.489135000 0.114045000 -2.468955000 C -5.212540000 -0.863359000 -3.318105000 H -5.996783000 -0.225931000 -2.896396000 H -4.972973000 -0.499422000 -4.325583000




13

H -5.624694000 -1.875022000 -3.424005000 C -2.928095000 -1.861261000 -3.064026000 H -2.669692000 -1.543784000 -4.082586000 H -2.009791000 -1.905719000 -2.467574000 H -3.350568000 -2.872748000 -3.123635000 C -3.487718000 -0.178125000 2.652353000 H -3.130370000 0.804586000 2.331236000 C -2.291902000 -0.914058000 3.274258000 H -1.465274000 -1.005053000 2.560683000 H -1.931052000 -0.363686000 4.153070000 H -2.580905000 -1.921854000 3.600954000 C -4.575748000 0.026022000 3.715024000 H -4.859482000 -0.929251000 4.174674000 H -4.198669000 0.674567000 4.516232000 H -5.483112000 0.480121000 3.301209000 P2(CAAC)2

2+(2++) E = -2584.910077 P 0.816118000 0.036250000 -0.961506000 N 3.062472000 0.530826000 0.520138000 C 2.078134000 1.092190000 -0.096217000 C 2.226484000 2.581339000 -0.254839000 C 2.057414000 2.936285000 -1.751739000 H 1.056677000 2.617994000 -2.086081000 H 2.794834000 2.382031000 -2.351178000 C 2.189203000 4.442910000 -1.975979000 H 3.200341000 4.776150000 -1.697275000 H 2.074294000 4.657351000 -3.045596000 C 1.146595000 5.202296000 -1.157734000 H 1.256139000 6.282649000 -1.310076000 H 0.140591000 4.929884000 -1.513412000 C 1.265053000 4.864743000 0.327197000 H 0.474132000 5.363806000 0.900681000 H 2.218685000 5.247333000 0.718654000 C 1.166905000 3.355181000 0.567424000 H 0.165486000 3.017204000 0.258843000 H 1.269825000 3.127079000 1.636048000 C 3.684460000 2.786416000 0.227091000 H 4.348191000 2.857006000 -0.645000000 H 3.806022000 3.703753000 0.811442000 C 4.064347000 1.553250000 1.066952000 C 3.212142000 -0.921798000 0.510173000 C 3.748446000 -1.499268000 -0.666920000 C 3.800597000 -2.895292000 -0.728792000 H 4.214765000 -3.370365000 -1.616529000 C 3.357512000 -3.684712000 0.325021000




14

H 3.423271000 -4.769884000 0.257527000 C 2.847742000 -3.087914000 1.472348000 H 2.519169000 -3.715871000 2.298690000 C 2.754556000 -1.698403000 1.594791000 C 3.816334000 1.795623000 2.555548000 H 2.780374000 2.088003000 2.760514000 H 4.470310000 2.618440000 2.868277000 H 4.071619000 0.921212000 3.158568000 C 5.492832000 1.080632000 0.852109000 H 5.672928000 0.120466000 1.352624000 H 6.166423000 1.824115000 1.295355000 H 5.742145000 0.990619000 -0.208640000 C 4.310805000 -0.714442000 -1.846665000 H 4.209013000 0.358519000 -1.639213000 C 5.806396000 -1.023381000 -2.028945000 H 6.367101000 -0.924202000 -1.092967000 H 6.241941000 -0.346466000 -2.774458000 H 5.946563000 -2.048899000 -2.392503000 C 3.566621000 -1.009819000 -3.156966000 H 4.000245000 -0.414743000 -3.970373000 H 2.497476000 -0.774671000 -3.093838000 H 3.666007000 -2.066743000 -3.434300000 C 2.216777000 -1.124555000 2.894684000 H 2.068723000 -0.046773000 2.760256000 C 0.865150000 -1.724932000 3.299058000 H 0.109808000 -1.600266000 2.513915000 H 0.499617000 -1.229857000 4.207234000 H 0.950537000 -2.795632000 3.521865000 C 3.233803000 -1.354762000 4.025401000 H 3.277110000 -2.421005000 4.282196000 H 2.938092000 -0.804079000 4.927350000 H 4.248445000 -1.050582000 3.742134000 P -0.650449000 0.185644000 0.442097000 N -3.160578000 -0.566541000 -0.220057000 C -1.927529000 -0.944651000 -0.312507000 C -1.783692000 -2.361735000 -0.831128000 C -0.827946000 -3.193009000 0.050462000 H 0.166094000 -2.721938000 0.058842000 H -1.197883000 -3.200251000 1.086571000 C -0.682607000 -4.617706000 -0.485867000 H -1.650162000 -5.139800000 -0.444083000 H 0.000522000 -5.176049000 0.166833000 C -0.160724000 -4.601676000 -1.921742000 H -0.067090000 -5.624260000 -2.306707000 H 0.848875000 -4.160023000 -1.932402000 C -1.078011000 -3.781655000 -2.827211000 H -0.666660000 -3.723517000 -3.842602000




15

H -2.052540000 -4.281704000 -2.918031000 C -1.258766000 -2.358201000 -2.291671000 H -0.278355000 -1.863475000 -2.322906000 H -1.931048000 -1.781372000 -2.939289000 C -3.245499000 -2.862151000 -0.726289000 H -3.367969000 -3.428287000 0.206494000 H -3.520696000 -3.522358000 -1.554464000 C -4.154376000 -1.624532000 -0.692512000 C -3.553250000 0.743124000 0.279975000 C -3.827397000 0.876356000 1.661372000 C -4.237260000 2.133085000 2.111615000 H -4.461365000 2.271025000 3.168077000 C -4.363184000 3.210067000 1.241412000 H -4.699096000 4.175698000 1.616130000 C -4.047576000 3.058226000 -0.102722000 H -4.130663000 3.914008000 -0.770534000 C -3.627506000 1.828950000 -0.620094000 C -4.710108000 -1.238930000 -2.062082000 H -3.933586000 -1.135656000 -2.826020000 H -5.395562000 -2.033569000 -2.379553000 H -5.282842000 -0.308353000 -1.998671000 C -5.315352000 -1.772889000 0.280667000 H -5.874474000 -0.834729000 0.382999000 H -5.996463000 -2.526983000 -0.132603000 H -4.991052000 -2.119121000 1.265350000 C -3.646016000 -0.231357000 2.690986000 H -3.348819000 -1.151646000 2.170504000 C -4.940884000 -0.508470000 3.470131000 H -5.803482000 -0.658507000 2.812793000 H -4.817990000 -1.401639000 4.095423000 H -5.174197000 0.328703000 4.139564000 C -2.526938000 0.121109000 3.683569000 H -2.372705000 -0.712295000 4.380973000 H -1.577839000 0.332699000 3.177962000 H -2.799173000 1.004393000 4.274775000 C -3.245655000 1.765417000 -2.092417000 H -2.961942000 0.736015000 -2.339565000 C -2.027848000 2.659362000 -2.367563000 H -1.191216000 2.403777000 -1.707545000 H -1.701674000 2.546226000 -3.409580000 H -2.276365000 3.716229000 -2.206821000 C -4.403232000 2.182685000 -3.010410000 H -4.627364000 3.250097000 -2.892412000 H -4.127380000 2.018624000 -4.059536000 H -5.324749000 1.628000000 -2.804006000

P2(NHC)2(4)




16

E = -3000.598323 P -1.078772000 -0.146087000 -0.077918000 N -3.083051000 1.681666000 -0.220473000 N -1.239193000 2.709480000 -0.751951000 C -1.719169000 1.476858000 -0.355458000 C -3.425462000 2.986368000 -0.529389000 H -4.452420000 3.329196000 -0.483213000 C -2.284955000 3.626718000 -0.858820000 H -2.099596000 4.648902000 -1.167202000 C -3.969064000 0.704057000 0.317700000 C -4.588645000 -0.204347000 -0.554106000 C -5.436698000 -1.163930000 0.005656000 H -5.937599000 -1.881523000 -0.643367000 C -5.650003000 -1.211132000 1.380348000 H -6.314728000 -1.965903000 1.799560000 C -5.024669000 -0.295842000 2.223313000 H -5.205536000 -0.341011000 3.297128000 C -4.165515000 0.678975000 1.709345000 C 0.116719000 3.109900000 -0.976899000 C 0.771112000 3.841393000 0.029671000 C 2.079102000 4.261509000 -0.221790000 H 2.626382000 4.809646000 0.542095000 C 2.692766000 3.986596000 -1.439426000 H 3.712383000 4.326305000 -1.619794000 C 2.014703000 3.278464000 -2.426296000 H 2.508454000 3.071291000 -3.372726000 C 0.716216000 2.813135000 -2.211069000 C -4.378924000 -0.127376000 -2.055965000 H -3.569530000 0.589291000 -2.239296000 C -5.645455000 0.396698000 -2.743768000 H -6.486846000 -0.292810000 -2.588487000 H -5.480705000 0.495637000 -3.824968000 H -5.935772000 1.378238000 -2.346795000 C -3.932757000 -1.468174000 -2.641593000 H -3.023293000 -1.814357000 -2.137574000 H -3.720320000 -1.355201000 -3.713668000 H -4.710483000 -2.237517000 -2.533932000 C -3.501791000 1.690333000 2.630302000 H -2.824673000 2.303823000 2.023941000 C 0.108622000 4.104826000 1.372283000 H -0.974370000 4.169669000 1.205232000 C 0.552266000 5.421942000 2.012576000 H 0.456447000 6.264378000 1.315383000 H 1.594915000 5.372476000 2.353053000 H -0.066316000 5.630073000 2.895000000 C 0.365371000 2.928020000 2.321544000




17

H -0.018341000 1.988175000 1.903766000 H -0.115647000 3.108662000 3.293199000 H 1.445083000 2.803249000 2.481412000 C -0.032789000 2.028184000 -3.274232000 H -0.689504000 1.319265000 -2.750471000 C -0.902713000 2.963150000 -4.125461000 H -0.273041000 3.699936000 -4.643469000 H -1.632072000 3.506127000 -3.512075000 H -1.453501000 2.387902000 -4.881938000 C 0.901478000 1.206877000 -4.164215000 H 0.308516000 0.551642000 -4.814702000 H 1.564948000 0.582107000 -3.551693000 H 1.511683000 1.848872000 -4.814249000 P 1.110108000 0.176460000 -0.196973000 N 3.090339000 -1.614661000 0.308532000 N 1.230852000 -2.737931000 0.116748000 C 1.726885000 -1.449391000 0.094096000 C 3.412216000 -2.958337000 0.426157000 H 4.428209000 -3.284396000 0.613959000 C 2.265976000 -3.655069000 0.296902000 H 2.068711000 -4.720461000 0.309568000 C 3.952361000 -0.548480000 0.708417000 C 3.995652000 -0.213913000 2.071722000 C 4.829478000 0.842018000 2.451988000 H 4.887603000 1.130320000 3.501417000 C 5.582554000 1.530182000 1.506008000 H 6.224563000 2.352620000 1.819843000 C 5.521491000 1.176509000 0.159918000 H 6.112492000 1.729654000 -0.567369000 C 4.701074000 0.129824000 -0.266398000 C -0.097045000 -3.202160000 -0.149908000 C -0.417292000 -3.581643000 -1.460993000 C -1.672212000 -4.156618000 -1.684497000 H -1.953744000 -4.457651000 -2.693323000 C -2.572100000 -4.324056000 -0.639144000 H -3.550142000 -4.764651000 -0.830507000 C -2.242980000 -3.906778000 0.648262000 H -2.975480000 -4.011450000 1.445024000 C -0.996911000 -3.340348000 0.921905000 C 3.173818000 -0.960992000 3.110270000 H 2.634910000 -1.768183000 2.600521000 C 4.076063000 -1.605165000 4.168449000 H 4.614107000 -0.843237000 4.748523000 H 3.473245000 -2.197912000 4.869325000 H 4.819615000 -2.266721000 3.705391000 C 2.118908000 -0.052305000 3.749518000 H 1.454166000 0.352181000 2.977366000




18

H 1.517958000 -0.623233000 4.471378000 H 2.586900000 0.785733000 4.285033000 C 4.622220000 -0.294408000 -1.722978000 H 3.595458000 -0.648078000 -1.890763000 C 5.593756000 -1.448232000 -2.006382000 H 5.379900000 -2.322479000 -1.381091000 H 5.522682000 -1.756876000 -3.058053000 H 6.626792000 -1.129925000 -1.809321000 C 4.880731000 0.857934000 -2.693052000 H 4.639977000 0.541910000 -3.716594000 H 4.258593000 1.723184000 -2.440806000 H 5.935929000 1.164313000 -2.683924000 C 0.526660000 -3.329964000 -2.622879000 H 1.456488000 -2.909963000 -2.221043000 C 0.876334000 -4.622418000 -3.366650000 H 1.330835000 -5.358364000 -2.690776000 H -0.017217000 -5.078357000 -3.813782000 H 1.586404000 -4.412551000 -4.177427000 C -0.077722000 -2.281880000 -3.564570000 H -0.314798000 -1.364927000 -3.008762000 H 0.631225000 -2.037303000 -4.366893000 H -1.002092000 -2.656996000 -4.026053000 C -0.626550000 -2.859364000 2.315994000 H -0.021595000 -1.950308000 2.184111000 C 0.211602000 -3.898624000 3.073852000 H -0.351806000 -4.835866000 3.181752000 H 1.154930000 -4.119591000 2.561749000 H 0.451607000 -3.525681000 4.079304000 C -1.855049000 -2.476262000 3.140930000 H -1.537096000 -1.969816000 4.061420000 H -2.508482000 -1.799379000 2.576762000 H -2.431095000 -3.363902000 3.437749000 C -4.553171000 2.621254000 3.246602000 H -4.068798000 3.385417000 3.868917000 H -5.252402000 2.059116000 3.880602000 H -5.137072000 3.128084000 2.467276000 C -2.648161000 1.016396000 3.707776000 H -2.192385000 1.777999000 4.354466000 H -1.847396000 0.429641000 3.242417000 H -3.248857000 0.350582000 4.342452000 P2(NHC)2

+(4+.) E = -3000.447823 P -1.062595000 -0.088397000 0.437841000 P 0.914861000 -0.016024000 -0.371809000 N 1.484578000 -1.996262000 1.707526000




19

N 3.090129000 -1.552759000 0.325202000 N -1.447669000 2.304154000 -1.191489000 N -2.936903000 0.760839000 -1.455586000 C 1.804396000 -1.224375000 0.636988000 C 2.556427000 -2.795552000 2.058553000 H 2.503283000 -3.472205000 2.903498000 C 3.560660000 -2.518614000 1.189540000 H 4.569625000 -2.906927000 1.110357000 C 0.293738000 -1.897755000 2.504422000 C -0.773050000 -2.770989000 2.238597000 C -1.900065000 -2.662544000 3.055176000 H -2.749346000 -3.322390000 2.886444000 C -1.958955000 -1.709426000 4.069165000 H -2.850926000 -1.637344000 4.690449000 C -0.890001000 -0.848044000 4.295579000 H -0.953014000 -0.107861000 5.092440000 C 0.271088000 -0.930268000 3.521975000 C 3.906835000 -0.911411000 -0.671875000 C 4.748119000 0.135043000 -0.259185000 C 5.571185000 0.714362000 -1.229933000 H 6.236617000 1.529975000 -0.950536000 C 5.553368000 0.261496000 -2.544342000 H 6.206633000 0.721682000 -3.284464000 C 4.706437000 -0.777423000 -2.921551000 H 4.709517000 -1.122091000 -3.953759000 C 3.862502000 -1.389093000 -1.991884000 C -0.713602000 -3.787775000 1.111903000 H 0.058278000 -3.453205000 0.405299000 C -0.308019000 -5.166053000 1.650815000 H 0.670643000 -5.138193000 2.145718000 H -0.258929000 -5.896225000 0.832886000 H -1.046388000 -5.519471000 2.382978000 C -2.033205000 -3.871200000 0.339663000 H -2.824065000 -4.340345000 0.939810000 H -1.898651000 -4.486021000 -0.559824000 H -2.374366000 -2.874718000 0.031851000 C 1.443608000 -0.002846000 3.797736000 H 2.252641000 -0.257107000 3.101940000 C 1.068951000 1.462527000 3.549117000 H 0.727543000 1.616227000 2.517019000 H 1.939316000 2.108056000 3.725520000 H 0.268729000 1.782215000 4.229769000 C 1.978502000 -0.207498000 5.220051000 H 1.226015000 0.071638000 5.969111000 H 2.863799000 0.420032000 5.384659000 H 2.257959000 -1.254190000 5.394729000 C 4.771271000 0.657545000 1.167641000




20

H 4.179281000 -0.022343000 1.792220000 C 4.113131000 2.040268000 1.241120000 H 4.653758000 2.760702000 0.611448000 H 4.128167000 2.414245000 2.273694000 H 3.071177000 2.000306000 0.898835000 C 6.192168000 0.682452000 1.741013000 H 6.672107000 -0.301272000 1.664135000 H 6.163867000 0.972543000 2.798947000 H 6.823887000 1.410350000 1.216030000 C 2.982439000 -2.561998000 -2.385477000 H 2.172902000 -2.636613000 -1.647477000 C 3.793205000 -3.864750000 -2.345672000 H 4.622124000 -3.819742000 -3.064613000 H 3.157240000 -4.720340000 -2.606794000 H 4.219200000 -4.044063000 -1.350509000 C 2.332283000 -2.366369000 -3.756156000 H 3.074989000 -2.392552000 -4.563670000 H 1.796728000 -1.409322000 -3.801709000 H 1.617233000 -3.176668000 -3.944901000 C -1.777506000 1.044247000 -0.819514000 C -2.392288000 2.799640000 -2.068145000 H -2.323326000 3.803173000 -2.470897000 C -3.328353000 1.830022000 -2.234224000 H -4.230899000 1.796843000 -2.833914000 C -3.672401000 -0.476035000 -1.365676000 C -3.506495000 -1.420116000 -2.387830000 C -4.285253000 -2.580526000 -2.319440000 H -4.188078000 -3.337531000 -3.096507000 C -5.175475000 -2.781618000 -1.272078000 H -5.775098000 -3.690161000 -1.237889000 C -5.298774000 -1.833567000 -0.258116000 H -5.991307000 -2.014713000 0.560902000 C -4.550780000 -0.655119000 -0.281213000 C -0.456184000 3.131084000 -0.548994000 C 0.781585000 3.340571000 -1.178057000 C 1.703025000 4.146487000 -0.505395000 H 2.676420000 4.334578000 -0.954060000 C 1.398243000 4.706900000 0.732504000 H 2.137694000 5.323179000 1.242412000 C 0.150583000 4.503135000 1.312294000 H -0.083928000 4.971966000 2.267243000 C -0.816453000 3.720740000 0.673816000 C -2.511783000 -1.239788000 -3.520708000 H -2.032913000 -0.258677000 -3.412272000 C -1.405305000 -2.297350000 -3.432773000 H -0.865533000 -2.219211000 -2.479325000 H -0.689077000 -2.157868000 -4.251812000




21

H -1.822766000 -3.309833000 -3.515442000 C -3.207204000 -1.268853000 -4.886121000 H -3.659601000 -2.249843000 -5.080490000 H -2.481023000 -1.071796000 -5.684793000 H -4.001233000 -0.513627000 -4.946221000 C -4.705046000 0.399968000 0.802330000 H -3.743314000 0.919458000 0.898212000 C -5.014982000 -0.201841000 2.173324000 H -4.950721000 0.580190000 2.940632000 H -4.296152000 -0.990987000 2.424081000 H -6.030155000 -0.617199000 2.215405000 C -5.770309000 1.432728000 0.409365000 H -5.529690000 1.926451000 -0.540305000 H -5.854655000 2.205949000 1.184720000 H -6.749116000 0.946849000 0.301262000 C 1.088771000 2.787528000 -2.559887000 H 0.438817000 1.917040000 -2.723831000 C 2.536964000 2.316886000 -2.709435000 H 3.238328000 3.161835000 -2.704232000 H 2.658776000 1.801046000 -3.670550000 H 2.818045000 1.620610000 -1.910761000 C 0.765561000 3.842497000 -3.628761000 H -0.283239000 4.160588000 -3.591302000 H 0.967798000 3.443792000 -4.631103000 H 1.389967000 4.733564000 -3.480512000 C -2.214278000 3.602508000 1.264101000 H -2.814574000 2.959098000 0.609053000 C -2.215828000 2.963652000 2.656073000 H -1.791911000 1.952144000 2.626235000 H -3.245406000 2.900152000 3.033492000 H -1.635510000 3.565237000 3.368532000 C -2.894890000 4.977685000 1.285734000 H -2.370607000 5.667086000 1.960259000 H -3.929633000 4.881463000 1.639399000 H -2.910228000 5.429850000 0.285880000 P2(NHC)2

2+(4++) E = -3000.151256 P 0.144093000 0.484420000 0.887292000 N -2.277045000 -0.263087000 2.226138000 N -2.484525000 1.619624000 1.182821000 C -1.644630000 0.595091000 1.408477000 C -3.537946000 0.207708000 2.500094000 H -4.219163000 -0.331983000 3.149292000 C -3.668987000 1.394918000 1.841806000 H -4.486595000 2.106795000 1.801074000




22

C -1.687902000 -1.422210000 2.860215000 C -1.799543000 -2.664238000 2.215450000 C -1.251258000 -3.765375000 2.876527000 H -1.310988000 -4.750703000 2.418503000 C -0.657848000 -3.624308000 4.129125000 H -0.256727000 -4.500593000 4.637039000 C -0.593341000 -2.380938000 4.749680000 H -0.143710000 -2.295832000 5.737873000 C -1.107452000 -1.239295000 4.127165000 C -2.159881000 2.852838000 0.499478000 C -1.685895000 3.918835000 1.283245000 C -1.409802000 5.114283000 0.611985000 H -1.041649000 5.972002000 1.173283000 C -1.608070000 5.226025000 -0.760175000 H -1.393689000 6.170088000 -1.259644000 C -2.102684000 4.152572000 -1.498031000 H -2.277702000 4.271008000 -2.565466000 C -2.407395000 2.937855000 -0.880091000 C -2.572897000 -2.829271000 0.919572000 H -2.630362000 -1.847965000 0.425808000 C -4.007268000 -3.286853000 1.224023000 H -3.993833000 -4.263795000 1.724399000 H -4.582382000 -3.384686000 0.294896000 H -4.531851000 -2.582424000 1.881368000 C -1.892712000 -3.793779000 -0.050378000 H -0.842413000 -3.523032000 -0.213486000 H -2.415277000 -3.782635000 -1.015004000 H -1.921329000 -4.825662000 0.322616000 C -1.083157000 0.100876000 4.845305000 H -1.458180000 0.870895000 4.158170000 C -2.024369000 0.065365000 6.057485000 H -3.046210000 -0.209650000 5.766983000 H -2.054360000 1.048135000 6.544053000 H -1.677729000 -0.667229000 6.797650000 C 0.332885000 0.514583000 5.259762000 H 0.302883000 1.488469000 5.764070000 H 0.998434000 0.596459000 4.391827000 H 0.772350000 -0.205585000 5.961615000 C -1.495371000 3.826795000 2.789580000 H -1.876384000 2.854935000 3.128833000 C -2.307662000 4.907715000 3.513971000 H -3.366511000 4.872773000 3.229339000 H -1.928254000 5.911325000 3.285108000 H -2.234705000 4.766281000 4.599304000 C -0.013441000 3.899193000 3.176444000 H 0.559555000 3.072526000 2.736256000 H 0.092618000 3.848857000 4.267494000




23

H 0.435639000 4.842091000 2.837764000 C -3.083594000 1.813101000 -1.644326000 H -2.921686000 0.875174000 -1.092801000 C -4.597813000 2.066384000 -1.704923000 H -4.803344000 3.001910000 -2.241040000 H -5.039694000 2.151250000 -0.704589000 H -5.101002000 1.248307000 -2.235089000 C -2.513532000 1.625078000 -3.049169000 H -2.949420000 0.728744000 -3.507951000 H -1.421901000 1.518771000 -3.030673000 H -2.760088000 2.473134000 -3.700707000 P -0.144093000 -0.484420000 -0.887292000 N 2.277045000 0.263087000 -2.226138000 N 2.484525000 -1.619624000 -1.182821000 C 1.644630000 -0.595091000 -1.408477000 C 3.537946000 -0.207708000 -2.500094000 H 4.219163000 0.331983000 -3.149292000 C 3.668987000 -1.394918000 -1.841806000 H 4.486595000 -2.106795000 -1.801074000 C 1.687902000 1.422210000 -2.860215000 C 1.799543000 2.664238000 -2.215450000 C 1.251258000 3.765375000 -2.876527000 H 1.310988000 4.750703000 -2.418503000 C 0.657848000 3.624308000 -4.129125000 H 0.256727000 4.500593000 -4.637039000 C 0.593341000 2.380938000 -4.749680000 H 0.143710000 2.295832000 -5.737873000 C 1.107452000 1.239295000 -4.127165000 C 2.159881000 -2.852838000 -0.499478000 C 1.685895000 -3.918835000 -1.283245000 C 1.409802000 -5.114283000 -0.611985000 H 1.041649000 -5.972002000 -1.173283000 C 1.608070000 -5.226025000 0.760175000 H 1.393689000 -6.170088000 1.259644000 C 2.102684000 -4.152572000 1.498031000 H 2.277702000 -4.271008000 2.565466000 C 2.407395000 -2.937855000 0.880091000 C 2.572897000 2.829271000 -0.919572000 H 2.630362000 1.847965000 -0.425808000 C 4.007268000 3.286853000 -1.224023000 H 3.993833000 4.263795000 -1.724399000 H 4.582382000 3.384686000 -0.294896000 H 4.531851000 2.582424000 -1.881368000 C 1.892712000 3.793779000 0.050378000 H 0.842413000 3.523032000 0.213486000 H 2.415277000 3.782635000 1.015004000 H 1.921329000 4.825662000 -0.322616000




24

C 1.083157000 -0.100876000 -4.845305000 H 1.458180000 -0.870895000 -4.158170000 C 2.024369000 -0.065365000 -6.057485000 H 3.046210000 0.209650000 -5.766983000 H 2.054360000 -1.048135000 -6.544053000 H 1.677729000 0.667229000 -6.797650000 C -0.332885000 -0.514583000 -5.259762000 H -0.302883000 -1.488469000 -5.764070000 H -0.998434000 -0.596459000 -4.391827000 H -0.772350000 0.205585000 -5.961615000 C 1.495371000 -3.826795000 -2.789580000 H 1.876384000 -2.854935000 -3.128833000 C 2.307662000 -4.907715000 -3.513971000 H 3.366511000 -4.872773000 -3.229339000 H 1.928254000 -5.911325000 -3.285108000 H 2.234705000 -4.766281000 -4.599304000 C 0.013441000 -3.899193000 -3.176444000 H -0.559555000 -3.072526000 -2.736256000 H -0.092618000 -3.848857000 -4.267494000 H -0.435639000 -4.842091000 -2.837764000 C 3.083594000 -1.813101000 1.644326000 H 2.921686000 -0.875174000 1.092801000 C 4.597813000 -2.066384000 1.704923000 H 4.803344000 -3.001910000 2.241040000 H 5.039694000 -2.151250000 0.704589000 H 5.101002000 -1.248307000 2.235089000 C 2.513532000 -1.625078000 3.049169000 H 2.949420000 -0.728744000 3.507951000 H 1.421901000 -1.518771000 3.030673000 H 2.760088000 -2.473134000 3.700707000 Full reference for Gaussian 03 in ref. 43: Gaussian 03, Revision E.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M.

A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.;

Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G.

A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,

T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.;

Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;

Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.;

Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick,

D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford,




25

S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.;

Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M.

W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford

CT, 2004.

supplementary information · 2010-04-23 · final r indices [i>2sigma(i)] r1 = 0.0593, wr2 =...

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