Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany
Rhodium(I) Complexes of a PBP Ambiphilic Ligand: Evidence for a Metal Borane Interaction** Sébastien Bontemps, Heinz Gornitzka, Ghenwa Bouhadir, Karinne Miqueu, Didier Bourissou* Contents Computational details S1 Results. S4 Z-matrix and total ZPE energy.... S6 Spectroscopic data.......s13 -S1-
Computational details Calculations were performed with the Gaussian 98 program, [1,2] using the density functional method. [3] The hybrid exchange functional B3LYP and the gradient-corrected functional BP86 were used. B3LYP is a three parameter functional developed by Becke which combines the Becke gradient-corrected exchange functional [4a] and the Lee-Yang-Parr and Vosko-Wilk-Nusair correlation functionals [4b] with part of exact HF exchange energy. BP86 consists of Becke 88 gradient correction for exchange [5a] and Perdew 86 expression for the correlation energy. [5b] Different basis set were retained for all the calculations. The 6-31G* [6] basis set was used for C, P, B, Cl, N and H. Six basis set-recp (relativistic effective core potential) [LanL2DZ, [7] CEP-31G, [8] SDD, [9] LanL2DZ+f, CEP+f and SDD+f] were retained for Rh. The first and second basis sets, denoted as LanL2DZ and CEP-31G, are double ζ valence basis sets associated with the ECPs of Hay/Wadth and Stevens/Basch/Krauss, respectively. The third, denoted as SDD, is the combination of the Huzinaga-Dunning double ζ basis set on lighter elements with the Stuttgart/Dresden basis set-recp on transition metals. Finally, the fourth, fifth and sixth, denoted as LanL2DZ+f, CEP-31G+f and SDD+f, are respectively the LanL2DZ, CEP-31G and SDD basis sets augmented with an f-type polarization function with an exponent of 1.350 [10] [Rh(α c )=1.350]. The optimized structures were confirmed as true minima on the potential energy through vibrational analysis. The frequencies were calculated with analytical second derivative. All total energies have been zero-point energy (ZPE) and temperature corrected using unscaled density functional frequencies. The electronic structure of the model complex 4* was studied using Natural Bond Orbital (NBO) analysis. [11] The NBO-3.1 program was used to gain insight into the nature of the interaction between rhodium and boron and to evaluate the energy of donor/acceptor interaction (interaction between filled and empty orbitals). The Natural Localized Molecular Orbitals (NLMO) obtained from the NBO analysis was plotted by using the molecular graphic package Molekel. [12] -S2-
References [1] Gaussian 98, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratman, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. K. Rabuck, Raghavachari, J. B. Foresman, J. Cioslowswi, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. Martin, D. J. Fox, T. Keith, M. A. Al- Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Jonhson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian 98, Revision A.7, Gaussian, Inc., Pittsburgh PA, 1998. [2] W. J. Hehre, L. Radom, P.v.R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, John Wiley and Sons: New York, 1986. [3] R. G. Parr, W. Yang, Functional Theory of Atoms and Molecules, R. Breslow, J. B. Goodenough, Eds., Oxford University Press: New York, 1989. [4] a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-789. [5] a) A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; b) J. P. Perdew, Phys. Rev. 1986, B33, 8822-8824; c) J. P. Perdew, Phys. Rev. 1986, B34, 7406 (erratum). [6] a) G. A. Petersson, M. A. Al-Laham, J. Chem. Phys. 1991, 94, 6081-6090; b) G. A. Petersson, A. Bennett, T. G. Tensfeldt, M. A. Al-Laham, W. A. Shirley, J. Mantzaris, J. Chem. Phys. 1988, 89, 2193-2218. [7] a) T. H. Dunning Jr., P. J. Hay, In Modern Theoretical Chemistry, H. F. Schaefer III, Ed.; Plenum : New York, 1976, 1-28; b) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283; c) W. R. Wadt, P. J. Hay, J. Chem. Phys. 1985, 82, 284-298; d) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310. [8] a) W. Stevens, H. Basch, J. Krauss, J. Chem. Phys. 1984, 81, 6026-6033; B) W. Stevens, J. Krauss, H. Basch, J. Chem. Phys. 1992, 70, 612-630; c) T. R. Cunduri, W. Stevens, J. Chem. Phys., 1992, 98, 5555-5565. [9] a) M. Dolg, in Modern Methods and Algorithm of Quantum Chemistr; Grotendorst J., Ed.; John von Neuman Institute for Computing: Jülich, 2000, vol 1, pp 479-508; b) M. Dolg, U. Wedig, H. Stoll, H. Preuss, J. Chem. Phys. 1987, 86, 866-872; c) D. Andrae, U. Häussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim. Acta. 1990, 77, 123-141. [10] A. W. Ehlers, M. Böhme, S. Dapprich, A. Gobbi, A. Höllwarth, V. Jonas, K. F. Köhler, R. Stegmann, A. Veldkamp, G. Frenking, Chem. Phys. Lett. 1993, 208, 111-114. [11] a) A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926; b) J. P. Foster, F. Weinhold, J. Am. Chem. Soc. 1980, 102, 7211-7218. [12] a) P. F. Flükiger, Development of the molecular graphics package MOLEKEL and its application to selected problems in organic and organometallic chemistry, thèse, Université de Geneva, Suisse, 1992; b) S. Portmann, H. P. Lüthi, MOLEKEL: An Interactive Molecular Graphics Tool. Chimia, 54, 2000. -S3-
Results The structural parameters for the model complex 4* were determined at different levels of theory. The BP86 functional led to a significantly better agreement between the optimized geometry of 4* and the X-ray diffraction study of 4 than the B3LYP functional. At the BP86/6-31G*(C,P,B,Cl,N,P,H) level of theory, only marginal differences were observed for the various basis sets used for Rh (LanL2DZ, CEP-31G and SDD), and the addition of a f function did not induce noticeable variations. Table S1. Selected bond lengths and angles (in Å and, respectively) predicted for the model complex 4*. H 2 N B Ph Me 2 P Rh N 4* PMe 2 Cl N B P Rh N Cl P Rh-P Rh-B PRhP PRhB ΣRh α ΣB α X-ray 2.286(1)/2.256(1) 2.295(5) 97.62(4) 80.1(1)/83.6(1) 360.2 340.3 B3LYP/LanL2DZ(Rh)* 2.296/2.265 2.458 97.52 78.13/81.38 359.3 344.6 BP86/LanL2DZ(Rh)* 2.282/2.249 2.392 97.39 78.61/82.04 359.2 342.8 BP86/CEP-31G(Rh)* 2.281/2.251 2.384 97.38 78.51/81.97 359.2 339.2 BP86/SDD(Rh)* 2.274/2.241 2.381 97.41 78.63/82.10 359.2 342.2 BP86/LanL2DZ+f(Rh)* 2.279/2.244 2.392 97.33 78.59/82.07 359.2 342.8 BP86/CEP-31G+f(Rh)* 2.278/2.347 2.385 97.33 78.49/81.98 359.2 342.2 BP86/SDD+f(Rh)* 2.271/2.237 2.382 97.35 78.61/82.11 348.6 342.2 * The 6-31G* basis set was used for C,P,B,Cl,N,P,H. -S4-
Table S2. Stabilizing interaction dz2 (Rh) pπ (B) (kcal/mol) for complex 4* at different calculation levels. Hybridization of the NLMO involving the Rh and Boron atoms. dz2 (Rh) pπ (B) Acceptor NBO pπ (B) NLMO Rh B % dz2 (Rh) % pπ (B) % s (B) % p (B) B3LYP/LanL2DZ(Rh)* stabilizing interaction (kcal/mol) 34.8 81.8 14.9 11.6 88.3 BP86/LanL2DZ(Rh)* 29.6 81.1 15.6 12.2 87.7 BP86/CEP-31G (Rh)* 55.2 79.3 17.1 12.7 87.3 BP86/SDD (Rh)* 50.6 80.5 16.1 12.5 87.4 BP86/LanL2DZ+f (Rh)* 30.0 81.0 15.6 12.2 87.7 BP86/CEP-31G+f(Rh)* 57.6 79.9 16.7 12.7 87.2 BP86/SDD+f(Rh)* 50.1 80.1 16.3 12.6 87.4 * The 6-31G* basis set was used for C,P,B,Cl,N,P,H. Whatever the basis set, the stabilizing interaction dz2 (Rh) pπb is rather large (> 29.6 kcal/mol). Although the precise value for this donor-acceptor interaction is meaningless, its magnitude is in agreement with a strong interaction between the rhodium and boron atoms. The concerned NLMO has about 80 % contribution from the dz2 (Rh) orbital, with major delocalization tails (16 %) from the vacant boron orbital pπb. This transfer of electron density from the metal to the σ-acceptor ligand is accompanied by some hydridization of the boron atom (around 12 % s and 88 % p). Figure S1. Molekel plots (cutoff : 0.04) for the Donor NBO, Acceptor NBO and NLMO involving the rhodium and boron atoms at the BP86/[CEP-31G+f(Rh),6-31G*(C,P,B,Cl,N,P,H)] level of theory. B B Rh Rh Donor NBO dz2 (Rh) Acceptor NBO pπ (Β) -S5- NLMO dz2 (Rh) / pπ (Β)
Z-Matrix and ZPE total energy (ua) 4 * [B3LYP/LanL2DZ(Rh)/6-31G*(C,P,B,Cl,N,P,H)] C -0.657861-0.275142 2.800336 C -0.061681 0.745588 2.025696 C -0.470514 2.068422 2.302724 C -1.417210 2.361283 3.288780 C -1.989794 1.328853 4.034332 C -1.604374 0.007765 3.784249 B 1.048709 0.411790 0.932367 Rh -0.316979-0.644356-0.817753 Cl -0.769004-2.879433 0.099583 C 1.761378 1.698168 0.240468 C 1.336085 2.266475-0.977498 C 1.950693 3.407404-1.516280 C 3.015723 4.007998-0.849249 C 3.460827 3.461145 0.357945 C 2.843485 2.328470 0.887218 P -0.060209 1.394585-1.771407 C 2.105434-0.748243 1.304399 C 2.604651-1.629696 0.323008 C 3.609128-2.559727 0.606764 C 4.143102-2.634766 1.894052 C 3.661261-1.780440 2.886685 C 2.657564-0.853897 2.593431 P 1.775148-1.463564-1.292330 N -2.482713-0.332309-0.503299 C -3.266910-1.100189-1.287943 C -4.646902-1.134177-1.194163 C -5.293135-0.350500-0.220036 C -4.473722 0.439582 0.603983 C -3.098800 0.415401 0.429865 N -6.666823-0.326038-0.111389 C 0.230483 1.490491-3.601160 C 3.017630-0.584168-2.356861 C 1.775114-3.120813-2.103016 C -1.471364 2.587056-1.615144 H -7.171734-1.110858-0.500542 H -7.051238 0.006672 0.762609 H -2.457861 1.009958 1.068029 H -4.901252 1.062099 1.384568 H -5.216005-1.775900-1.860667 H -2.752086-1.727190-2.007105 H 2.286388-0.207643 3.385289 H 4.061285-1.842752 3.896210 H 4.916671-3.363473 2.122369 H 3.966648-3.241181-0.161884 H 3.215276 1.913992 1.821299 H 4.296790 3.916995 0.883526 H 3.498963 4.887108-1.267753 H 1.607367 3.824987-2.460499 H -0.023818 2.888750 1.746100 H -1.699445 3.394544 3.480187 H -2.723577 1.550466 4.806022 H -2.044849-0.804747 4.357560 H -0.388803-1.308716 2.603282 H 1.323003-3.025767-3.095928 H 2.793997-3.506648-2.217253 H 1.169089-3.802741-1.505018 H 2.694444-0.600380-3.403207 H 3.141234 0.451645-2.034372 H 3.984243-1.094554-2.285687 H -0.624817 1.038283-4.113655 H 0.333883 2.526395-3.942003 H 1.129261 0.935558-3.876582 H -2.359965 2.188997-2.114360 H -1.703305 2.742422-0.559156 H -1.205303 3.550173-2.063883 Etot(ZPE) : -2433.970304 ua -S6-
4 * [BP86/LanL2DZ(Rh)/6-31G*(C,P,B,Cl,N,P,H)] C -0.700722-0.329085 2.780949 C -0.096538 0.704354 2.013994 C -0.508301 2.032901 2.304658 C -1.464982 2.318718 3.294676 C -2.044756 1.273340 4.032461 C -1.656146-0.053287 3.769637 B 1.020558 0.377894 0.915483 Rh -0.299295-0.621657-0.810830 Cl -0.729272-2.871148 0.040629 C 1.757265 1.684614 0.275321 C 1.336037 2.285900-0.937495 C 1.953074 3.443703-1.455490 C 3.023584 4.030436-0.766552 C 3.466572 3.453082 0.436913 C 2.843102 2.302779 0.943478 P -0.065273 1.414167-1.737189 C 2.085073-0.779149 1.299932 C 2.610418-1.635822 0.299041 C 3.624471-2.570583 0.568621 C 4.141972-2.675550 1.869907 C 3.635226-1.847333 2.884175 C 2.622918-0.914351 2.600723 P 1.780011-1.415201-1.316550 N -2.449227-0.344946-0.495986 C -3.225531-1.126840-1.292539 C -4.614286-1.162348-1.217975 C -5.281525-0.368286-0.253767 C -4.470388 0.433380 0.582462 C -3.085167 0.413230 0.429631 N -6.661624-0.342791-0.168745 C 0.211221 1.534941-3.575030 C 3.025217-0.494260-2.353410 C 1.784589-3.049385-2.187490 C -1.483739 2.605527-1.556457 H -7.163152-1.138258-0.562620 H -7.063330-0.001492 0.703953 H -2.445716 1.015937 1.079652 H -4.913556 1.063884 1.360642 H -5.175500-1.816097-1.894447 H -2.690944-1.764230-2.002319 H 2.230015-0.285769 3.409440 H 4.024219-1.936600 3.905928 H 4.924199-3.410430 2.092733 H 4.000707-3.233231-0.220884 H 3.213418 1.861083 1.876971 H 4.309065 3.900514 0.978305 H 3.514435 4.924856-1.167335 H 1.609114 3.884245-2.400168 H -0.050351 2.863410 1.752904 H -1.749705 3.359065 3.496892 H -2.787793 1.489646 4.809762 H -2.102864-0.877696 4.338898 H -0.427942-1.369511 2.570181 H 1.334698-2.920003-3.186985 H 2.813560-3.432534-2.307056 H 1.169200-3.752877-1.606950 H 2.710250-0.491151-3.411546 H 3.132020 0.542855-2.000464 H 4.003329-1.001645-2.280583 H -0.661709 1.099506-4.090660 H 0.328630 2.583993-3.900316 H 1.107051 0.965929-3.865522 H -2.383651 2.208045-2.054930 H -1.703427 2.748042-0.486893 H -1.218249 3.581048-2.000388 Etot(ZPE) : -2434.108959 ua -S7-
4 * [BP86/CEP-31G(Rh)/6-31G*(C,P,B,Cl,N,P,H)] C -0.672545-0.301670 2.797565 C -0.085945 0.723580 2.006253 C -0.509129 2.052742 2.277442 C -1.459747 2.346503 3.271077 C -2.021953 1.308888 4.032943 C -1.621539-0.018103 3.790220 B 1.022806 0.388569 0.899983 Rh -0.302346-0.644304-0.792036 Cl -0.715610-2.864105 0.084077 C 1.745209 1.695865 0.241130 C 1.309069 2.278286-0.975707 C 1.910244 3.435487-1.513021 C 2.980370 4.040993-0.839848 C 3.438370 3.482712 0.367016 C 2.830092 2.332785 0.892729 P -0.090953 1.380976-1.750789 C 2.106067-0.748285 1.298047 C 2.632119-1.615071 0.306291 C 3.660499-2.532615 0.580099 C 4.192003-2.609924 1.877710 C 3.684481-1.771877 2.883620 C 2.658039-0.855875 2.595380 P 1.778481-1.428587-1.302341 N -2.446977-0.370422-0.475985 C -3.227340-1.152870-1.269460 C -4.616133-1.180663-1.196450 C -5.280605-0.378386-0.237253 C -4.466256 0.423578 0.595535 C -3.081159 0.396233 0.444882 N -6.660504-0.345171-0.154295 C 0.172845 1.478626-3.592879 C 3.002349-0.514477-2.370799 C 1.792656-3.078753-2.144383 C -1.516381 2.567282-1.581527 H -7.166251-1.139308-0.545372 H -7.062057 0.003986 0.715331 H -2.439586 1.000556 1.091154 H -4.906819 1.060463 1.369959 H -5.179624-1.834747-1.870593 H -2.695408-1.795021-1.976898 H 2.264992-0.219389 3.397878 H 4.084516-1.839986 3.902779 H 4.985566-3.331306 2.104624 H 4.037613-3.203078-0.202444 H 3.211928 1.906468 1.828731 H 4.280723 3.944922 0.896130 H 3.459409 4.935028-1.255568 H 1.554512 3.861276-2.460157 H -0.064648 2.878013 1.707147 H -1.753302 3.387415 3.457312 H -2.760316 1.531387 4.812934 H -2.054443-0.836764 4.378180 H -0.389959-1.342938 2.604627 H 1.324493-2.973418-3.138203 H 2.824464-3.450654-2.274345 H 1.196957-3.781108-1.542512 H 2.674480-0.533792-3.424840 H 3.103425 0.529914-2.037945 H 3.986396-1.010592-2.300607 H -0.698996 1.027836-4.097046 H 0.278960 2.523840-3.934063 H 1.072163 0.913758-3.880636 H -2.417362 2.157841-2.068374 H -1.730394 2.726266-0.513095 H -1.259152 3.537081-2.042434 Etot(ZPE) : -2434.710409ua -S8-
4 * [BP86/SDD(Rh)/6-31G*(C,P,B,Cl,N,P,H)] C -0.676463-0.275931 2.802717 C -0.086744 0.741549 2.003545 C -0.506914 2.073822 2.264436 C -1.458562 2.377492 3.254070 C -2.025009 1.347079 4.022620 C -1.626642 0.017412 3.791462 B 1.020566 0.395297 0.898774 Rh -0.301222-0.644982-0.787210 Cl -0.722017-2.854465 0.105722 C 1.746604 1.695635 0.230481 C 1.313992 2.265965-0.993280 C 1.918593 3.416154-1.541671 C 2.988968 4.026035-0.872900 C 3.443106 3.479977 0.341039 C 2.831223 2.337197 0.878001 P -0.086709 1.362700-1.759125 C 2.100387-0.741796 1.305585 C 2.624047-1.616562 0.319561 C 3.648061-2.537249 0.599672 C 4.177976-2.609012 1.898207 C 3.673696-1.762083 2.898346 C 2.651645-0.843226 2.603759 P 1.770951-1.436968-1.289510 N -2.437942-0.368437-0.476159 C -3.216854-1.156672-1.265980 C -4.605598-1.186179-1.193893 C -5.272132-0.380254-0.238866 C -4.459582 0.428109 0.589627 C -3.074335 0.402302 0.440048 N -6.651651-0.350544-0.155609 C 0.173950 1.443707-3.602443 C 2.998572-0.535402-2.364879 C 1.781603-3.092689-2.121186 C -1.509241 2.553781-1.601855 H -7.156273-1.146887-0.543533 H -7.054764 0.004149 0.711001 H -2.434123 1.010126 1.084263 H -4.901482 1.068105 1.360715 H -5.167237-1.845823-1.864211 H -2.683035-1.802805-1.968693 H 2.261930-0.199490 3.402112 H 4.073136-1.825173 3.918065 H 4.968083-3.332513 2.130342 H 4.022241-3.214374-0.178543 H 3.209699 1.920566 1.819779 H 4.285072 3.946418 0.867072 H 3.470745 4.914633-1.297037 H 1.565941 3.832410-2.494170 H -0.059864 2.893768 1.688346 H -1.749612 3.420585 3.431866 H -2.764020 1.577381 4.799705 H -2.061618-0.795697 4.385624 H -0.397277-1.319585 2.617514 H 1.299841-2.996425-3.109526 H 2.814093-3.459131-2.261345 H 1.197240-3.794601-1.507913 H 2.675608-0.569522-3.420149 H 3.098309 0.513372-2.045648 H 3.981944-1.031083-2.282976 H -0.700298 0.991203-4.101130 H 0.281269 2.486499-3.950850 H 1.071204 0.874842-3.888516 H -2.412332 2.139240-2.080650 H -1.720777 2.729711-0.535574 H -1.249755 3.515614-2.078070 Etot(ZPE) : -2435.193795 ua -S9-
4 * [BP86/LanL2DZ+f (Rh)/6-31G*(C,P,B,Cl,N,P,H)] C -0.697692-0.314164 2.785570 C -0.095263 0.715155 2.011792 C -0.507149 2.045164 2.295421 C -1.462573 2.336172 3.285130 C -2.040859 1.294730 4.029630 C -1.651932-0.033190 3.773961 B 1.020726 0.383189 0.913679 Rh -0.300392-0.626225-0.806136 Cl -0.728190-2.867591 0.056739 C 1.755833 1.686449 0.265283 C 1.333101 2.279072-0.951174 C 1.948615 3.433993-1.477217 C 3.019000 4.026351-0.792847 C 3.463326 3.457557 0.414195 C 2.841341 2.310024 0.928859 P -0.068272 1.399716-1.742798 C 2.085705-0.771564 1.303240 C 2.609546-1.632980 0.305777 C 3.623999-2.566343 0.578441 C 4.143360-2.664831 1.879529 C 3.638147-1.831580 2.890443 C 2.625341-0.900041 2.603931 P 1.775995-1.418656-1.309177 N -2.444094-0.349459-0.492871 C -3.221106-1.134496-1.286105 C -4.609828-1.168630-1.211882 C -5.276928-0.369764-0.251535 C -4.465444 0.435214 0.581151 C -3.080243 0.413531 0.428920 N -6.656949-0.343038-0.167041 C 0.205693 1.508841-3.581989 C 3.021851-0.503826-2.351230 C 1.781244-3.056778-2.173423 C -1.486011 2.593746-1.569778 H -7.159070-1.139701-0.557702 H -7.058909 0.002930 0.703686 H -2.440774 1.019085 1.076190 H -4.908350 1.069719 1.356210 H -5.171174-1.825054-1.885634 H -2.686928-1.775496-1.992929 H 2.233678-0.267420 3.410100 H 4.028714-1.915760 3.912027 H 4.925922-3.398585 2.104895 H 3.999109-3.232840-0.208364 H 3.212635 1.874949 1.865072 H 4.305697 3.909471 0.952041 H 3.508734 4.918551-1.199905 H 1.603638 3.867942-2.424566 H -0.050442 2.872656 1.738157 H -1.747529 3.377511 3.481804 H -2.782980 1.515125 4.806655 H -2.097413-0.854518 4.348613 H -0.424519-1.355635 2.580551 H 1.329160-2.932272-3.172562 H 2.810592-3.438740-2.293630 H 1.168344-3.759149-1.588970 H 2.708074-0.507947-3.409723 H 3.128207 0.535665-2.005306 H 3.999967-1.010535-2.274025 H -0.668505 1.071098-4.093537 H 0.323551 2.555730-3.914012 H 1.100465 0.937195-3.870465 H -2.386635 2.193622-2.064872 H -1.705093 2.744524-0.501211 H -1.219913 3.565767-2.020961 Etot(ZPE) : -2434.111267 ua -S10-
4 * [BP86/CEP-31G+f(Rh)/6-31G*(C,P,B,Cl,N,P,H)] C -0.668641-0.286393 2.802231 C -0.083940 0.734397 2.003839 C -0.507179 2.064970 2.267864 C -1.456310 2.364183 3.261276 C -2.016853 1.330826 4.030133 C -1.616177 0.002609 3.794726 B 1.023416 0.393624 0.897790 Rh -0.303911-0.648755-0.786881 Cl -0.714790-2.859500 0.100892 C 1.744291 1.697247 0.230574 C 1.306236 2.271426-0.989407 C 1.906017 3.425510-1.534796 C 2.976565 4.035981-0.866743 C 3.436328 3.485834 0.343178 C 2.829415 2.338917 0.877017 P -0.094452 1.367365-1.755815 C 2.107166-0.740979 1.300584 C 2.631312-1.612693 0.312284 C 3.660030-2.528957 0.588892 C 4.193799-2.599678 1.885977 C 3.688257-1.756381 2.888502 C 2.661365-0.841736 2.597485 P 1.774005-1.432698-1.295274 N -2.442055-0.374288-0.472616 C -3.223011-1.159244-1.263493 C -4.611745-1.186109-1.190736 C -5.276162-0.380159-0.234567 C -4.461580 0.424462 0.595402 C -3.076515 0.396078 0.445243 N -6.656004-0.346095-0.152030 C 0.165801 1.454058-3.599189 C 2.997832-0.524890-2.369637 C 1.788142-3.086809-2.130255 C -1.519023 2.556165-1.592720 H -7.162143-1.141226-0.540556 H -7.057742 0.006638 0.716060 H -2.434972 1.002798 1.089208 H -4.901960 1.064490 1.367323 H -5.175275-1.842324-1.862758 H -2.691376-1.804095-1.968697 H 2.269904-0.201053 3.397419 H 4.090184-1.819302 3.907251 H 4.987662-3.320002 2.115218 H 4.035628-3.203427-0.190938 H 3.212577 1.918868 1.815312 H 4.278998 3.951996 0.868304 H 3.454587 4.927609-1.288770 H 1.548912 3.845029-2.484202 H -0.064017 2.886985 1.691888 H -1.750057 3.406039 3.441813 H -2.754119 1.557607 4.809927 H -2.047702-0.812724 4.388294 H -0.385751-1.328647 2.615157 H 1.317184-2.986455-3.123286 H 2.820131-3.457772-2.261514 H 1.195229-3.787720-1.524016 H 2.669963-0.550636-3.423552 H 3.099125 0.521519-2.043331 H 3.981809-1.020705-2.296518 H -0.707404 1.000901-4.098901 H 0.271781 2.497170-3.946788 H 1.064127 0.886965-3.885614 H -2.421050 2.144288-2.075603 H -1.731622 2.722850-0.525160 H -1.261668 3.522582-2.060599 Etot(ZPE) : -2434.712662 ua -S11-
4 * [BP86/SDD+f(Rh)/6-31G*(C,P,B,Cl,N,P,H)] Rh -0.303048-0.649711-0.781644 Cl -0.721739-2.849226 0.124787 P -0.089772 1.347891-1.765034 P 1.766102-1.442231-1.281531 N -2.433044-0.372275-0.472360 N -6.647238-0.351372-0.153531 B 1.021230 0.401028 0.896312 C -0.672224-0.258509 2.807795 C -0.084611 0.753834 2.000638 C -0.504812 2.087639 2.253406 C -1.454906 2.397497 3.242592 C -2.019560 1.371976 4.018965 C -1.620850 0.040992 3.796190 C 1.745871 1.697146 0.218885 C 1.311576 2.258293-1.008439 C 1.915075 3.404706-1.565763 C 2.985813 4.019941-0.902464 C 3.441395 3.483042 0.315017 C 2.830647 2.343891 0.860902 C 2.101414-0.733751 1.308504 C 2.622791-1.614351 0.326618 C 3.646867-2.533867 0.610158 C 4.179152-2.598239 1.908134 C 3.677239-1.745125 2.904222 C 2.655012-0.827555 2.606231 C -3.212423-1.163451-1.259254 C -4.601120-1.191999-1.187652 C -5.267760-0.381947-0.236178 C -4.455112 0.429451 0.589224 C -3.069875 0.402563 0.440365 C 0.168010 1.416348-3.609524 C 2.993952-0.547932-2.363241 C 1.776493-3.102448-2.105024 C -1.511337 2.541771-1.615221 H -7.152186-1.148877-0.538617 H -7.050651 0.007235 0.711318 H -2.429742 1.013058 1.082056 H -4.896987 1.072943 1.357402 H -5.162674-1.854123-1.855579 H -2.678781-1.812656-1.959263 H 2.267183-0.178914 3.401536 H 4.078623-1.802369 3.923522 H 4.969291-3.320794 2.143113 H 4.019192-3.215692-0.164842 H 3.210226 1.934317 1.805334 H 4.283660 3.953715 0.836781 H 3.466783 4.905640-1.333536 H 1.561246 3.813910-2.520863 H -0.059044 2.903843 1.671057 H -1.746162 3.441612 3.413900 H -2.757380 1.607142 4.795722 H -2.054293-0.768274 4.396681 H -0.392592-1.303215 2.629352 H 1.291658-3.011803-3.092410 H 2.809077-3.468088-2.246551 H 1.195080-3.802481-1.486859 H 2.671058-0.589102-3.418313 H 3.094147 0.502978-2.051299 H 3.977141-1.043392-2.278050 H -0.707399 0.960996-4.103608 H 0.275210 2.456657-3.965311 H 1.064415 0.845054-3.893482 H -2.415501 2.124431-2.089589 H -1.721495 2.726430-0.550104 H -1.251802 3.499663-2.099275 Etot(ZPE) : -2435.196090 ua -S12-
Spectroscopic data for 2-4 11 B, 31 P and 103 Rh chemical shifts are expressed with a positive sign, in parts per million, relative to external BF 3.OEt 2, 85% H 3 PO 4 and Ξ = 3,186447 MHz. Otherwise stated, NMR was recorded at 293 K. 10 9 11 5 6 8 B 7 12 6 5 4 3 1 2 1 2 3 4 P P 2: 31 P{ 1 H} NMR (C 6 D 6 ) δ = 11.0; 13 C{ 1 H} NMR (C 6 D 6 ) δ = 160.4 (d, 1 J C-P = 43.0 Hz, C 2 ), 147.7 (s, C 7 ), 137.4 (s br, C 1 ), 137.3 (s, C 8 and C 12 ), 136.0 (pseudo-t, J C-P = 25.0 Hz, C 3 or 6 ), 131.0 (s, C 3 or 6 ), 129.2 (s, C 10 ), 128.7 (s, C 4 or 5 ), 127.6 (s, C 9 and C 11 ), 126.8 (s, C 4 or 5 ), 25.7 (pseudo-t, 1 J C-P = 4.0 Hz, CHCH 3 ), 20.3 (pseudo-t, 2 J C-P = 3.8 Hz, CHCH 3 ), 20.1 (pseudo-t, 2 J C-P = 6.6 Hz, CHCH 3 ); 1 H NMR (C 6 D 6 ) δ = 8.62 (d, 2H, 3 J H-H = 7.2 Hz, H 3 or 6 ), 7.79 (d, 2H, 3 J H-H = 5.6 Hz, H 8 and H 12 ), 7.56 (pseudo-t, 2H, 3 J H-H = 7.2 Hz, H 4 or 5 ), 7.43 (dd, 2H, 3 J H-H = 7.2 Hz, J H-P = 5.2 Hz, H 3 or 6 ), 7.32 (pseudo-t, 2H, 3 J H-H = 7.2 Hz, H 4 or 5 ), 7.25 (m, 3H, H 9, H 10 and H 11 ), 2.04 ( sept.d, 4H, 3 J H-H = 7.0 Hz, 2 J H-P = 14.0 Hz, CHCH 3 ), 1.06 (dd, 12H, 3 J H-H = 7.0 Hz, 3 J H-P = 13.8 Hz, CHCH 3 ), 0.87 (dd, 12H, 3 J H-H = 7.0 Hz, 3 J P-H = 13.8 Hz, CHCH 3 ); 11 B NMR (C 6 D 6 ) δ = 43.1; MS (EI, 70eV) m/z (%): 474 [M] + (5), 431 [M - i-pr] + (40), 388 [M - 2(i-Pr)] + (5), 357 [M - P(i-Pr) 2 ] + (10); mp: 95-97 C. -S13-
4 5 3 10 9 11 6 8 7 12 6 1 B 1 2 2 P Rh P 2 Cl 5 4 3 3: 31 P{ 1 H} NMR (CDCl 3, 293 K) δ = 88.8 (d, 1 J P-Rh = 187.0 Hz), 70.0 (br ν 1/2 650 Hz), 50.4 (d, 1 J P-Rh = 126.1 Hz); 11 B NMR (CDCl 3, 293 K) δ = 20,0; 31 P{ 1 H} NMR (CDCl 3, 213 K) δ = 50.0 (br, minor conformer), 74.7 (dd, 1 J P-Rh = 151.9 Hz, 2 J P-P = 24.3 Hz, P A ), 64.2 (dd, 1 J P-Rh = 160.0 Hz, 2 J P-P = 24.3 Hz, P B ), 100.0 (br, minor conformer); 13 C{ 1 H} NMR (CDCl 3, 213 K) δ = 168.4 (d, 2 J C-P = 41.5 Hz, C 1B ), 167.5 (d, 2 J C-P = 38.5 Hz, C 1A ), 156.0 (s br, C 7 ), 140.3 (d, 1 J C-P = 51.6 Hz, C 2A ), 138.8 (d, 1 J C-P = 49.1 Hz, C 2B ), 138.2 (s, C 8 or 12 ), 135.5 (s, C 8 or 12), 131.9 (s, C 3A or 6A ), 131.0 (d, J C-P = 20.0 Hz, C 3B or 6B ), 129.0 (s, C 3B or 6B ), 128.8 (s, C 4B or 5B), 128.5 (s, C 3A or 6A ), 127.5 (s, C 9 or 10 or 11 and C 4A or 5A ), 125.9 (s, C 9 or 10 or 11 ), 124.8 (s, C 9 or 10 or 11), 123.9 (s, C 5B or 4B ), 123.4 (s, C 5A or 4A ), 30.1 (d, 1 J C-P = 22.6 Hz, P A CHCH 3 ), 28.5 (s br, P A CHCH 3 ), 27.8 (d, 1 J C-P = 10.7 Hz, P A CHCH 3 ), 26.6 (s br, P B CHCH 3 ), 25.1 (d, 1 J C-P = 18.9 Hz, P B CHCH 3 ), 24.8 (s, P B CHCH 3 ), 22.0 (s, P B CHCH 3 ), 21.5 (d, 2 J C-P = 6.3 Hz, P A CHCH 3 ), 21.4 (s, P B CHCH 3 ), 21.0 (d, 2 J C-P = 5.0 Hz, P A CHCH 3 ), 19.9 (s, P A CHCH 3 ), 18.8 (s, P B CHCH 3 ); 1 H NMR (CDCl 3, 213 K) δ = 8.57 (d, 1H, 3 J H-H = 7.0 Hz, H 8 ), 7.55 (m, 1H, H 6A ), 7.53 (d, 1H, 3 J H-H = 7.0 Hz, H 3A ), 7.25 (m, 4H, H 9 or 10 or 11, H 3B, H 4A and H 4B ), 7.12 (pseudo-t, 1H, 3 J H-H = 7.0 Hz, H 9 or 10 or 11 ), 7.05 (pseudo-t, 1H, 3 J H-H = 7.5 Hz, H 5A ), 7.00 (m, 1H, H 5B ), 6.93 (pseudo-t, 1H, 3 J H-H = 7.0 Hz, H 9 or 10 or 11 ), 6.85 (m, 1H, H 6B ), 6.55 (d, 1H, 3 J H-H = 7.0 Hz, H 12 ), 2.67 (br, 1H, P B CHCH 3 ), 2.27 (br, 1H, P A CHCH 3 ), 2.09 (br, 1H, P A CHCH 3 ), 1.92 (dd, 3H, 3 J H-P = 17.1 Hz, 3 J H-H = 6.6 Hz, P A CHCH 3 ), 1.74 (dd, 3H, 3 J H-P = 18.8 Hz, 3 J H-H = 6.4 Hz, P A CHCH 3 ), 1.60 (dd, 6H, 3 J H-P = 11.7 Hz, 3 J H-H = 6.7 Hz, P B CHCH 3 ), 1.13 (dd, 3H, 3 J H-P = 15.1 Hz, 3 J H-H = 6.7 Hz, P A CHCH 3 ), 1.05 (m, 1H, P B CHCH 3 ), 0.86 (dd, 3H, 3 J H-P = 14.7 Hz, 3 J H-H = 6.5 Hz, P B CHCH 3 ), 0.30 (dd, 6H, 3 J H-P = 14.0 Hz, 3 J H-H = 5.4 Hz, P A CHCH 3 and P B CHCH 3 ); 103 Rh NMR (CDCl 3, 213 K) δ = -7365; 31 P{ 1 H} NMR (solid state, 293 K) δ = 76.9 (d, 1 J P-Rh = 166.6 Hz), 66.5 (d, 1 J P-Rh =162.8 Hz); MS (DCI/NH 3 ) m/z (%): 1242 [M + NH 4 ] + (0.5), 1189 [M - Cl] + (1), 630 [M/2 + NH 4 ] + (20), 595 [(M/2 + NH 4 ) - Cl] + (10), 577 [M/2 - Cl] + (100); mp: 205 C ; elemental analysis calcd (%) for C 30 H 41 BClP 2 Rh: C 58.80, H 6.74; found: C 58.99, H 7.11. -S14-
4 5 3 10 9 11 6 8 7 12 6 1 B 1 2 2 P Rh P Cl N 13 17 14 16 15 N 5 4 3 4: 31 P{ 1 H} NMR (CDCl 3 ) δ = 66.8 (dd, 1 J P-Rh = 169.8 Hz, 2 J P-P = 31.0 Hz), 65.3 (dd, 1 J P-Rh = 144.5 Hz, 2 J P-P = 31.0 Hz); 13 C{ 1 H} NMR (CDCl 3 ) δ = 169.1 (d, 2 J C-P = 35.9 Hz, C 1B ), 166.9 (d, 2 J C-P = 40.8 Hz, C 1A ), 154.6 (s br, C 7 ); 153.2 (s, C 15 ), 150.0 (s, C 17 ), 148.8 (s, C 13 ), 141.0 (s, C 8 ), 140.9 (d, 1 J C-P = 47.7 Hz, C 2B ), 139.9 (d, 1 J C-P = 48.2 Hz, C 2A ), 135.7 (s, C 12 ), 132.2 (d, 3 J C-P = 21.1 Hz, C 6A ), 131.2 (d, 3 J C-P = 20.7 Hz, C 6B ), 128.6 (s, C 3A and C 3B ), 128.5 (s, C 4A or 5A), 128.0 (s, C 9 ), 127.5 (d, J C-P = 2.3 Hz, C 4B or 5B ), 126.0 (s, C 11 ), 125.4 (s, C 10 ), 123.7 (d, J C-P = 6.2 Hz, C 4A or 5A ), 123.6 (d, J C-P = 6.5 Hz, C 4B or 5B ), 107.3 (s,c 16 ), 106.0 (s, C 14 ), 39.0 (s, N(CH 3 ) 2 ), 29.7 (d, 1 J C-P = 20.4 Hz, P A CHCH 3 ), 28.2 (d, 1 J C-P = 28.4 Hz, P B CHCH 3 ), 27.7 (d, 1 J C-P = 21.3 Hz, P A CHCH 3 ), 26.2 (d, 2 J C-P = 5.0 Hz, P A CHCH 3 ), 26.1 (s, P B CHCH 3 ), 25.1 (d, 1 J C-P = 18.6 Hz, P B CHCH 3 ), 21.7 (d, 2 J C-P = 6.2 Hz, P B CHCH 3 ), 21.5 (d, 2 J C-P = 6.8 Hz, P A CHCH 3 ), 21.3 (d, 2 J C-P = 4.9 Hz, P B CHCH 3 ), 21.1 (d, 2 J C-P = 7.3 Hz, P A CHCH 3 ), 18.8 (s, P B CHCH 3 ), 17.5 (s, P A CHCH 3 ); 1 H NMR (CDCl 3 ) δ = 8.42 (d, 1H, 3 J H-H = 6.8 Hz, H 13 ), 8.40 (d, 1H, 3 J H-H = 7.2 Hz, H 8 ), 7.61 (pseudo-t, 1H, 3 J H-H = 6.7, 3 J H-P = 6.7 Hz, H 3A ), 7.51 (dd, 1H, 3 J H-H = 7.0 Hz, 3 J H-P = 7.3 Hz, H 3B ), 7.41 (d, 1H, 3 J H-H = 7.3 Hz, H 6B ), 7.29 (pseudo-t, 1H, 3 J H- H = 7.2 Hz, H 9 ), 7.25 (pseudo-t, 1H, 3 J H-H = 7.2 Hz, H 10 ), 7.18 (pseudo-t, 1H, 3 J H-H = 7.3 Hz, H 4B or 5B ), 7.14 (pseudo-t, 1H, 3 J H-H = 7.2 Hz, H 11 ), 7.04 (m, 4H, H 4A, H 5A, H 6A and H 4B or 5B ), 6.97 (d, 1H, 3 J H-H = 7.2 Hz, H 12 ), 6.38 (dd, 1H, 3 J H-H = 6.8 Hz, 4 J H-H = 3.2 Hz, H 14 ), 5.94 (d, 1H, 3 J H-H = 5.3 Hz, 4 J H-H = 3.2 Hz, H 16 ), 5.22 (d, 1H, 3 J H-H = 5.3 Hz, H 17 ), 3.58 ( sept.d, 1H, 2 J H-P = 10.8 Hz, 3 J H-H = 7.3 Hz, P B CHCH 3 ), 2.91 (s, 6H, N(CH 3 ) 2 ), 2.45 (sept.d, 1H, 2 J H-P = 7.5 Hz, 3 J H-H = 7.5 Hz, P A CHCH 3 ), 2.21 (sept.d, 1H, 2 J H-P = 7.6 Hz, 3 J H-H = 7.6 Hz, P A CHCH 3 ), 1.94 (dd, 3H, 3 J H-P = 17.1 Hz, 3 J H-H = 7.5 Hz, P A CHCH 3 ), 1.91 (dd, 3H, 3 J H-P = 16.6 Hz, 3 J H-H = 7.3 Hz, P B CHCH 3 ), 1.77 (dd, 3H, 3 J H-P = 10.0 Hz, 3 J H-H = 7.5 Hz, P A CHCH 3 ), 1.74 (dd, 3H, 3 J H-P = 11.3 Hz, 3 J H-H = 7.3 Hz, P B CHCH 3 ), 1.28 (m, 1H, P B CHCH 3 ), 1.18 (dd, 3H, 3 J H-P = 12.9 Hz, 3 J H-H = 7.2 Hz, P B CHCH 3 ), 1.10 (dd, 3H, 3 J H-P = 12.1 Hz, 3 J H-H = 7.6 Hz, P A CHCH 3 ), 0.47 (dd, 6H, 3 J H-P = 13.1 Hz, 3 J H-H = 7.6 Hz, P A CHCH 3 and P B CHCH 3 ); 11 B NMR (CDCl 3 ) δ = 19.4; 103 Rh NMR (CDCl 3 ) δ = -7552.2; mp: 137 C. -S15-