J. Am. Chem. Soc., 1997, 119(2), , DOI: /ja962545s

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J. Am. Chem. Soc., 1997, 119(2), 343-352, DOI:10.

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1 J. Am. Chem. Soc., 1997, 119(2), , DOI: /ja962545s Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machinereadable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at Copyright 1997 American Chemical Society

2 vi/ American onemicai zociety J. Am. k-nem. 3oc. V I I!) rage-,, ivoariguez 3uppiemental rage i Solution of 3: All measurements were made on an Siemens-SMART (Siemens Molecular Analysis Research lool) CCD (Charge-Coupled Device) diffractometer with graphite monochromated Mo-Kct radiation. An initial 360* rotation frame was acquired for a screening of the crystal. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using reflections observed within 15 frames at 5 sec/frame in the range 0 < 20 < 50 corresponded to a primitive monoclinic cell. For Z = 4 and F.W. = , the calculated density is 1.18 g/cm 3. Based on the systematic absences hol (1 2n) and OkO (k * 2n), packing considerations, a statistical analysis of intensity distribution, and the successful solution and refinement of the structure, the space group was determined to be P 21/c (# 14). The data were collected at a temperature of -50 ± I *C with an X-ray power of 50 kv and 30 ma. Scans of 0.30 were made at a speed of 1.8/min (in omega). The diameter of the incident beam collimator was 0.5 mm and the crystal to detector distance was 6.06 cm. The data collection hemisphere was set up into four separate runs. Omega was varied between to , and 0 was varied from 00 to was set at Data collection time was approximately 8 h with 1321 frames acquired at a rate of 10 sec/frame. SAINT 1 was used to perform the integration of intensity of reflections and scaling, absorption and time decay correction and statistical analysis of the data. The data were corrected for Lorentz and polarization effects. Of the reflections which were collected, were unique (Rint = 0.043); equivalent reflections were merged. An average decay correction of 1.008% was applied. The structure was solved by heavy-atom Patterson methods. Expansion of the structures with DIRDIF 2 revealed all the non-hydrogen atoms. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were refined isotropically. A toluene molecule of crystallization was found in the E-map and refined isotropically. The two

3 vi/ American onemicai zociety J. Am. k-nem. 30c. v I I!) rage-,, ivoariguez 3uppiementai rage L TMEDA's of one of the Li(TMEDA)2+ countercations was severely disordered and caused high residual electron density in this area of the E-map. This problem was treated by modeling one of the TMEDA's over two sites and constraining the occupancies to unity. The final cycle of full-matrix least-square refinement 3 was based on 9085 observed reflections (I > 3.00a(I)) and 806 variable parameters and converged (largest parameter shift was 0.24 times its esd) with unweighted and weighted agreement factors of R = and R( 1 = The standard deviation of an observation of unit weight 4 was The weighting scheme was based on counting statistics and included a factor (p = 0.010) to down weigh the most intense reflections. Plots of lm(ifo - IFcl) 2 versus IFol, reflection order in data collection, sin O/X and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 1.60 and e-la3, respectively. Neutral atom scattering factors were taken from Cromer and Waber. 5 Anomalous dispersion effects were included in Fcal; 6 the values for Af and Af' were those of Creagh and McAuley. 7 The values for the mass attenuation coefficients are those of Creagh and Hubbel. 8 All calculations were performed using the TEXSAN 9 crystallographic software package of Molecular Structure Corporation. 1 SAINT: Kabsch, J. Appl. Cryst. 1988, 21, DIRDIF92: Beurskens, P. T.; Admiraal, G.; beurskens, G.; Bosman, W. P.; Garcia-Granda, S.; Gould, R. 0.; Smits, J. M. M.; Smykalla, C The DIRDIF program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. 3 Least-Squares: Function minimized: mo(lfol - IFcl) 2 ; U -fo Gy2(Fo) SS 2 (C+R 2 B)+(pFo 2 ) 2 Lp2 _ 1 _4Fo 2 ) (y2&g2)

4 UI99I American Lhemical Society J. Am. Uhem. soc. V 1I V Fagei4i Kocriguez bupplemental Page - S = Scan rate C = Total integrated peak count R = Ratio of scan rime to background counting time B = Total background count Lp = Lorentz-polarization factor p = p-factor 4 Standard deviation of an observation of unit weight: V lw(ifol - IFcl) 2 / (No - Nv) where: No = number of observations Nv = number of variables 5 Cromer, D. T.; Waber, J. T., International Tables for X-ray Crystallography, Vol. IV, The Kynoch Press, Birmingham, England, 1974, Table 2.2A. 6 Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, Creagh, D. C.; McAuley, W. J., International Tables for Crystallography, Vol. C, Wilson, A. J. C. (ed.), Kluwer Academic Publishers, Boston, MA, 1992, Table , pp Creagh, D. C.; Hubbel, J. H., International Tables for Crystallography, Vol. C, Wilson, A. J. C. (ed.), Kluwer Academic Publishers, Boston, MA, 1992, Table , pp TEXSAN: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 and 1992).

5 V I VV American fiemical Society J. Am. Ulem. soc. V II V Fagei4i Kocriguez bupplemental Fage 4 Summary of Crystalographic Data for [Cp(TBM)ZrCl 2 ][Li(TMEDA)2] empirical formula color formula weight, amu crystal size, mm cryst syst space group z a, A b, A c, A v, A3 dcalc, g/cm 3 T, 'C scan type reflections collected -unique reflections agreement of equivalent data (Rin) no. of observations (I >3.00a(I)) no. of parameters varied abs coeff, cm- 1 p-factor radiation range of transm factors Ra; P,,b max Shift/error in final cycle goodness of fitc largest hole and peak in final E map ZrC39H55Cl2LiN4 burgundy x 0.30 x 0.23 monoclinic P21/c (No.14) (3) (3) (3) (1) (2) MoKa (X= A) ; ; 1.60 ar = Z(IFol - IFcI)/IFoI. brw = [Ym(lFol - IFcI) 2 /_)IFol 2 ] 1 /2 CS = goodness of fit = (IlFol - IFcl)/o)/(n-m), where n is the number of reflections used in the refinement and m is the number of variables

6 I VV / American fiemical society J. Am. ulem. soc. VI I VPage.54.5 Rocriguez bupplemental Page D Atomic coordinates and Biso/Beq atom x y z Beq Zr(1) (3) (3) (3) 2.75(1) Zr(2) (3) (4) (3) 3.05(1) Cl(1) (9) (1) (8) 4.55(5) Cl(2) (9) (9) (8) 4.12(4) CI(3) (1) (10) (9) 4.68(5) CI(4) (9) (1) (9) 4.67(5) N(1) (3) (4) (3) 5.0(2) N(2) (3) (4) (3) 5.6(2) N(3) (3) (3) (3) 5.0(2) N(4) (3) (3) (3) 4.2(1) N(5) (4) (5) (4) 8.7(2) N(6) (5) (6) (5) 10.9(3) N(7) (6) (6) (5) 3.3(2) N(8) (8) (9) (7) 6.9(4) N(9) (5) (6) (5) 2.7(2) N(10) 0.285(1) (1) 1.085(1) 14.8(8) C(1) (5) (5) (3) 6.2(2) C(2) (5) (5) (4) 6.3(2) C(3) (5) (4) (4) 5.8(2) C(4) (4) (5) (3) 5.2(2) C(5) (5) (4) (3) 5.7(2) C(6) (3) (3) (3) 3.0(1) C(7) (3) (4) (3) 3.4(2) C(8) (3) (4) (3) 3.3(2)

7 V I VV / American fiemical society J. Am. Ulem. soc. VI I VPage.54.5 Rocriguez bupplemental Page b Atomic coordinates and Biso/Beq (continued) atom x v z Beq C(9) (3) (3) (3) 3.3(2) C(10) (3) (4) (3) 3.5(2) C(11) (4) (4) (4) 4.5(2) C(12) (4) (5) (4) 5.6(2) C(13) (4) (4) (4) 5.8(2) C(14) (4) (5) (4) 6.0(2) C(15) (4) (4) (3) 4.7(2) C(16) (4) (4) (3) 3.7(2) C(17) (4) (4) (4) 4.8(2) C(18) (4) (4) (4) 5.4(2) C(19) (5) (4) (4) 5.9(2) C(20) (4) (4) (4) 5.2(2) C(21) (4) (4) (3) 4.8(2) C(22) (3) (4) (3) 3.3(2) C(23) (4) (4) (3) 4.3(2) C(24) (4) (5) (4) 5.9(2) C(25) (4) (6) (3) 6.3(2) C(26) (4) (5) (3) 5.9(2) C(27) (4) (4) (3) 4.6(2) C(28) (4) (6) (4) 6.5(3) C(29) (6) (5) (4) 7.8(3) C(30) (5) (5) (4) 7.1(3) C(31) (4) (6) (4) 6.8(3) C(32) (5) (5) (4) 6.5(2)

8 U I VV / American fiemical society J. Am. Ulem. soc. VI I Page.54.5 Rocriguez bupplemental Page / Atomic coordinates and Biso/Beq (continued) atom x y z Beq C(33) (3) (3) (3) 3.0(1) C(34) (3) (3) (3) 3.0(1) C(35) (3) (3) (3) 3.0(1) C(36) (3) (3) (3) 2.8(1) C(37) (3) (3) (3) 3.1(2) C(38) (4) (4) (3) 4.7(2) C(39) (4) (4) (4) 6.3(2) C(40) (4) (4) (4) 5.3(2) C(41) (4) (4) (4) 4.9(2) C(42) (4) (4) (3) 4.2(2) C(43) (3) (4) (3) 3.3(2) C(44) (4) (4) (3) 4.5(2) C(45) (5) (4) (3) 5.4(2) C(46) (4) (4) (3) 4.8(2) C(47) (4) (4) (4) 4.9(2) C(48) (4) (4) (3) 3.8(2) C(49) (3) (3) (3) 2.8(1) C(50) (4) (4) (3) 4.1(2) C(51) (4) (5) (3) 4.9(2) C(52) (4) (5) (3) 4.7(2) C(53) (4) (4) (3) 4.7(2) C(54) (3) (4) (3) 3.8(2) C(55) (5) (5) (4) 6.9(3) C(56) (4) (5) (4) 6.7(3)

9 V I VV9/ American fiemical society J. Am. Ulem. soc. VI I VPage.54.5 Rocriguez bupplemental Page z5 Atomic coordinates and Btso/Beq (continued) atom x y z Beq C(57) (4) (5) (4) 5.5(2) C(58) (4) (5) (4) 5.8(2) C(59) (5) (6) (4) 8.0(3) C(60) (5) (6) (4) 7.9(3) C(61) (5) (5) (4) 7.4(3) C(62) (5) (5) (4) 6.4(2) C(63) (4) (5) (4) 5.8(2) C(64) (4) (5) (4) 5.6(2) C(65) (5) (6) (5) 8.1(3) C(66) (5) (6) (5) 9.3(3) C(67) (9) (9) (8) 16.3(6) C(68) (5) (6) (5) 8.0(3) C(69) 0.308(1) 0.038(1) (10) 21.5(8) C(70) (9) 0.098(1) (8) 17.4(6) C(71) (5) (6) (5) 8.4(3) C(72) (8) (8) (7) 14.1(5) C(73) 0.154(2) 0.102(2) 0.967(1) 14(1) C(74) 0.159(1) 0.045(1) (9) 7.4(5) C(75) 0.208(1) 0.014(2) 1.055(1) 24(1) C(76) (10) (1) (9) 19.1(7) C(77) (8) (8) (7) 14.4(5) C(78) 0.370(1) 0.078(1) (10) 22.4(8) C(79) (6) (6) (5) 9.7(3) C(80) (9) 0.102(1) (8) 17.4(6)

10 I VV / American fiemical society J. Am. Ulem. soc. VI I VPage.54.5 Rocriguez bupplemental Page v Atomic coordinates and Biso/Beq (continued) atom x y z Beq C(81) 0.670(1) 0.111(1) 0.237(1) 25(1) C(82) (9) 0.119(1) (7) 15.4(6) C(83) 0.821(1) 0.095(1) (9) 18.1(7) C(84) 0.869(1) 0.070(1) (10) 21.1(8) C(85) (9) (1) (8) 17.0(6) C(86) (9) (1) (8) 17.4(6) C(87) (8) 0.056(1) (7) 14.0(5) Li(1) (6) (7) (6) 4.1(3) Li(2) (6) (7) (6) 4.3(3) H H H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(13)

11 v i u American onemicai 3ociety J. Am. Linem. 3oc. v II' rage-,, i-oariguez 3uppiemental rage iu Atomic coordinates and Biso/Beq (continued) atom x y z Bq H(14) H(15) H(16) H(17) H(18) H(19) H(20) H(21) H(22) -: H(23) H(24) H(25) H(26) H(27) H(28) H(29) H(30) H(31) H(32) H(33) H(34) H(35) H(36) H(37)

12 U I VV / American fiemical society J. Am. Ulem. soc. VI I Page.54.5 Rocriguez bupplemental Page II Atomic coordinates and Biso/Beq (continued) atom x y z Beq H(38) H(39) H(40) H(41) H(42) H(43) H(44) H(45) H(46) H(47) H(48) H(49) H(50) H(51) H(52) H(53) H(54) H(55) H(56) H(57) H(58) H(59) H(60) (61)

13 v i / american onemicai 3ociety J. Am. Linem. 3oC. vi i!) rage-,, i-oariguez 3uppiemental rage i/ Atomic coordinates and Biso/Beq (continued) atom x y z Beq H(62) H(63) H(64) H(65) H(66) H(67) H(68) H(69) H(70) H(71) H(72) H(73) H(74) B 3eq *)2 +2 U 22 (bb*) + U33+cc*) 2 + 2Ul 2 aa*bb* cos-y + 2U saa*cc* cosf + 2U 23 bb*cc* cos a)

14 I VV / American fiemical society J. Am. ulem. soc. VI I Page.54.5 Rocriguez bupplemental Page 1i Bond Lengths(A) atom atom distance atom atom distance Zr(1) C(1) 2.473(2) Zr(1) C1(2) 2.471(2) Zr(1) C(1) 2.494(7) Zr(1) C(2) 2.501(8) Zr(1) C(3) 2.505(8) Zr(1) C(4) 2.518(7) Zr(1) C(5) 2.500(7) Zr(1) C(6) 2.323(6) Zr(1) C(7) 2.422(7) Zr(1) C(8) 2.457(7) Zr(1) C(9) 2.597(6) Zr(2) C1(3) 2.471(2) Zr(2) C1(4) 2.477(2) Zr(2) C(28) 2.506(8) Zr(2) C(29) 2.514(8) Zr(2) C(30) 2.498(8) Zr(2) C(31) 2.502(8) Zr(2) C(32) 2.483(8) Zr(2) C(33) 2.336(6) Zr(2) 0(34) 2.460(6) Zr(2) C(35) 2.474(7) Zr(2) C(36) 2.537(6) N(1) C(55) 1.481(10) N(1) C(56) 1.48(1) N(1) C(57) 1.450(9) N(1) Li(1) 2.11(1) N(2) C(58) 1.51(1) N(2) C(59) 1.47(1) N(2) C(60) 1.44(1) N(2) Li(1) 2.09(1) N(3) C(61) 1.45(1) N(3) C(62) 1.475(10) N(3) C(63) 1.475(10) N(3) Li(1) 2.10(1) N(4) C(64) 1.464(10) N(4) C(65) 1.43(1) N(4) C(66) 1.44(1) N(4) Li(1) 2.13(1) N(5) C(67) 1.47(2) N(5) C(68) 1.50(1) N(5) ((69) 1.43(2) N(5) Li(2) 2.13(2) N(6) C(78) 1.40(2) N(6) C(79) 1.53(1) N(6) C(80) 1.34(2) N(6) Li(2) 2.11(2) N(7) N(8) 0.68(2) N(7) C(70) 1.31(2)

15 SI> I lha,1, I ~ f.1hi.u 3.JI.,1., J. JZxIII xx~xxx. J.Jt.- v xi - x J T. IJu.11 5 u.., J ujjji.,lhl.,ilui x U 5 '. I Bond Lengths(A) (continued) atom atom distance atom atom distance N(7) C(71) 1.50(2) N(7) C(72) 1.39(2) N(7) Li(2) 2.11(2) N(8) C(71) 1.39(2) N(8) C(72) 1.54(2) N(8) C(73) 1.51(3) N(8) Li(2) 1.97(2) N(9) N(10) 1.33(3) N(9) C(74) 1.68(2) N(9) C(75) 0.73(3) N(9) C(76) 1.52(2) N(9) C(77) 1.68(2) N(9) Li(2) 2.05(2) N(10) C(75) 1.72(3) N(10) C(76) 1.70(3) C(1) C(2) 1.36(1) C(1) -C(5) 1.40(1) C(2) C(3) 1.35(1) C(3) C(4) 1.34(1) C(4) C(5) 1.38(1) C(6) C(7) 1.435(9) C(6) C(8) 1.443(9) C(6) C(9) 1.408(9) C(7) C(10) 1.488(9) C(8) C(16) 1.475(9) C(9) C(22) 1.451(9) C(10) C(11) 1.379(9) C(10) C(15) 1.409(9) C(11) C(12) 1.39(1) C(12) C(13) 1.35(1) C(13) C(14) 1.36(1) C(14) C(15) 1.36(1) C(16) C(17) 1.383(10) C(16) C(21) 1.412(10) C(17) C(18) 1.39(1) C(18) C(19) 1.38(1) C(19) C(20) 1.36(1) C(20) C(21) 1.39(1) C(22) C(23) 1.388(10) C(22) C(27) 1.389(10) C(23) C(24) 1.38(1) C(24) C(25) 1.37(1) (25) C(26) 1.38(1) C(26) C(27) 1.38(1) C(28) C(29) 1.39(1) C(28) C(32) 1.36(1) C(29) C(30) 1.34(1) C(30) C(31) 1.36(1)

16 V I VV / American fiemical society J. Am. Ulem. soc. V 11 IPage.54.5 Rocriguez bupplemental Page 1D Bond Lengths(A) (continued) atom atom distance atom atom distance C(31) C(32) 1.36(1) C(33) C(34) 1.429(8) C(33) C(35) 1.471(8) C(33) C(36) 1.405(8) C(34) C(37) 1.451(9) C(35) C(43) 1.464(9) C(36) C(49) 1.459(8) C(37) C(38) 1.393(9) C(37) C(42) 1.393(9) C(38) C(39) 1.40(1) C(39) C(40) 1.37(1) C(40) C(41) 1.37(1) C(41) C(42) 1.368(10) C(43) C(44) 1.424(9) C(43) (48) 1.408(9) ((44) C(45) 1.40(1) C(45) C(46) 1.35(1) C(46) C(47) 1.38(1) C(47) C(48) 1.361(10) C(49) C(50) 1.398(9) C(49) C(54) 1.382(9) C(50) C(51) 1.403(10) C(51) C(52) 1.37(1) C(52) C(53) 1.33(1) C(53) C(54) 1.405(10) C(57) C(58) 1.48(1) C(63) C(64) 1.53(1) C(69) C(70) 1.70(3) C(72) C(73) 1.58(3) C(73) C(74) 1.83(4) C(74) C(75) 1.13(3) C(75) C(76) 1.58(3) C(77) C(78) 1.79(2) C(81) C(82) 1.63(3) C(81) C(87) 1.73(3) C(82) C(83) 1.33(2) C(82) C(87) 1.26(2) C(83) C(84) 1.06(3) C(83) C(87) 1.70(2) C(84) C(85) 1.53(3) C(85) C(86) 1.68(2) C(86) C(87) 1.49(2)

17 I VV9/ American fiemical society J. Am. ulem. soc. VI I Page.54.5 Rocriguez bupplemental Page 1 Bond Lengths(A) atom atom distance atom atom distance C(1) H(1) 0.97 C(2) H(2) 0.98 C(3) H(3) 1.00 C(4) H(4) 1.10 C(5) H(5) 0.98 C(7) H(22) 1.03 C(8) 11(23) 1.15 C(9) H(21) 0.98 C(11) H(6) 1.08 C(12) H(7) 0.99 C(13) H(8) 0.97 C(14) H(9) 0.98 C(15) H(10) 1.02 C(17) H(11) 1.12 C(18) H(12) 1.00 C(19) H(13) 1.00 C(20) -H(14) 0.98 C(21) H(15) 0.98 C(:23) H(20) 1.16 C(24) H(19) 0.98 C(25) H(18) 0.96 C(26) H(17) 1.00 C(27) H(16) 1.00 C(28) H(28) 0.98 C(29) H(24) 1.08 C(30) H(25) 0.99 C(31) H(26) 0.98 C(32) H(27) 1.00 C(34) H(44) 1.17 C(35) H(45) 1.09 C(36) 11(46) 0.98 C(38) H(29) 1.13 C(39) H(30) 0.89 C(40) H(31) 0.97 C(41) H(32) 0.96 C(42) H(33) 0.97 C(44) 11(34) 1.18 C(45) H(35) 0.91 C(46) H(36) 1.13 C(47) H(37) 1.17 C(48) H(38) 1.18 C(50) H(39) 1.13 C(51) H(40) 1.15 C(52) H(41) 0.89 C(53) 11(42) 0.99 C(54) 11(43) 1.06 C(55) H(50) 1.24 C(56) H(47) 0.90

18 ( 1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 17 Bond Lengths(A) (continued) atom atom distance atom atom distance C(56) H(48) 0.98 C(56) H(49) 0.95 C(57) H(51) 1.16 C(57) H(52) 1.23 C(58) H(53) 0.98 C(58) H(54) 0.94 C(59) H(55) 0.99 C(59) H(56) 0.97 C(59) H(57) 0.92 C(60) H(58) 0.98 C(60) H(59) 0.95 C(60) H(60) 0.96 C(61) H(61) 0.94 C(61) H(62) 0.98 C(61) H(63) 0.96 C(62) H 0.99 C(62) H(67) 0.92 C(62) H(68) 0.97 C(63) H 0.94 C(63) H(69) 0.96 C(64) H(70) 0.97 C(64) H(71) 0.97 C(65) H(72) 0.92 C(65) H(73) 1.00 C(65) H(74) 1.00 C(66) H(64) 1.00 C(66) H(65) 0.92 C(66) H(66) 0.96

19 ( 1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 18 Bond Angles( 0 ) atom atom atom angle atom atom atom angle Cl(1) Zr(1) Cl(2) 98.98(7) Cl(1) Zr(1) C(1) 126.9(2) Cl(1) Zr(1) C(2) 130.8(2) Cl(1) Zr(1) C(3) 100.7(2) Cl(1) Zr(1) C(4) 80.3(2) Cl(1) Zr(1) C(5) 94.3(2) Cl(1) Zr(1) C(6) 103.5(2) Cl(1) Zr(1) C(7) 138.5(2) Cl(1) Zr(1) C(8) 87.3(2) Cl(1) Zr(1) C(9) 83.8(2) Cl(2) Zr(1) C(1) 117.4(3) Cl(2) Zr(1) C(2) 87.2(2) Cl(2) Zr(1) C(3) 82.9(2) CI(2) Zr(1) C(4) 108.9(2) Cl(2) Zr(1) C(5) 134.7(2) Cl(2) Zr(1) C(6) 104.0(2) Cl(2) Zr(1) C(7) 91.9(2) Cl(2) Zr(1) C(8) 137.9(2) Cl(2) Zr(1) C(9) 81.7(2) C(1) Zr(1) C(2) 31.6(3) C(1) Zr(1) C(3) 52.1(3) C(1) Zr(1) C(4) 53.0(3) C(1) Zr(1) C(5) 32.6(3) C(1) Zr(1) C(6) 103.4(2) C(1) Zr(1) C(7) 80.3(2) C(1) Zr(1) C(8) 89.5(3) C(1) Zr(1) C(9) 135.6(2) C(2) Zr(1) C(3) 31.3(3) C(2) Zr(1) C(4) 52.0(3) C(2) Zr(1) C(5) 52.7(3) C(2) Zr(1) C(6) 122.4(3) C(2) Zr(1) C(7) 89.4(3) C(2) Zr(1) C(8) 119.7(3) C(2) Zr(1) C(9) 145.1(3) C(3) Zr(1) C(4) 30.9(3) C(3) Zr(1) C(5) 52.0(3) C(3) Zr(1) C(6) 153.4(3) C(3) Zr(1) C(7) 120.5(3) C(3) Zr(1) C(8) 137.1(2) C(3) Zr(1) C(9) 164.5(3) C(4) Zr(1) C(5) 31.9(3), C(4) Zr(1) C(6) 146.0(3) C(4) Zr(1) C(7) 133.3(2) C(4) Zr(1) C(8) 113.3(3) C(4) Zr(1) C(9) 162.0(2) C(5) Zr(1) C(6) 114.7(3) C(5) Zr(1) C(7) 106.0(3) C(5) Zr(1) C(8) 85.6(2)

20 V I VV / American fiemical society J. Am. Uhem. soc. VI 11' Fage.54.5 Rocriguez bupplemental Page 15' Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle C(5) Zr(1) C(9) 143.0(2) C(6) Zr(1) C(7) 35.1(2) C(6) Zr(1) C(8) 35.0(2) C(6) Zr(1) C(9) 32.7(2) C(7) Zr(1) C(8) 59.5(2) C(7) Zr(1) C(9) 58.2(2) C(8) Zr(1) C(9) 57.4(2) Cl(3) Zr(2) Cl(4) (7) Cl(3) Zr(2) C(28) 96.5(3) Cl(3) Zr(2) C(29) 78.6(2) Cl(3) Zr(2) C(30) 96.6(3) Cl(3) Zr(2) C(31) 127.6(3) Cl(3) Zr(2) C(32) 127.7(2) CI(3) Zr(2) C(33) 105.9(2) Cl(3) Zr(2) C(34) 94.2(2) CI(3) Zr(2) C(35) 140.0(1) Cl(3) Zr(2) C(36) 82.2(1) Cl(4) Zr(2) C(28) 134.2(2) Cl(4) Zr(2) C(29) 111.6(3) Cl(4) Zr(2) C(30) 83.9(3) Cl(4) Zr(2) C(31) 84.5(2) Cl(4) Zr(2) C(32) 113.9(3) CI(4) Zr(2) C(33) 103.6(2) Cl(4) Zr(2) C(34) 138.1(2) Cl(4) Zr(2) C(35) 85.8(2) Cl(4) Zr(2) C(36) 85.5(1) C(28) Zr(2) C(29) 32.2(3) C(28) Zr(2) C(30) 51.9(3) C(28) Zr(2) C(31) 52.2(3) C(28) Zr(2) C(32) 31.7(3) C(28) Zr(2) C(33) 112.3(3) C(28) Zr(2) C(34) 81.9(3) C(28) Zr(2) C(35) 107.4(3) C(28) Zr(2) C(36) 139.2(3) C(29) Zr(2) C(30) 31.0(3) C(29) Zr(2) C(31) 52.2(3) C(29) Zr(2) C(32) 53.0(3) C(29) Zr(2) C(33) 143.2(3) C(29) Zr(2) C(34) 109.7(3) C(29) Zr(2) C(35) 135.9(3) C(29) Zr(2) C(36) 156.2(3) C(30) Zr(2) C(31) 31.5(3) C(30) Zr(2) C(32) 52.3(3) C(30) Zr(2) C(33) 154.4(3) C(30) Zr(2) C(34) 133.4(3) C(30) Zr(2) C(35) 123.4(3) C(30) Zr(2) C(36) 168.9(3) C(31) Zr(2) C(32) 31.7(3)

21 I VV / American fiemical society J. Am. Uhem. soc. V 11 IPage.54.5 Rocriguez bupplemental Page 2U Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle C(31) Zr(2) C(33) 123.8(3) C(31) Zr(2) C(34) 116.6(3) C(31) Zr(2) C(35) 92.2(3) C(31) Zr(2) C(36) 149.8(3) C(32) Zr(2) C(33) 103.1(3) C(32) Zr(2) C(34) 86.0(3) C(32) Zr(2) C(35) 83.0(2) C(32) Zr(2) C(36) 136.3(3) C(33) Zr(2) C(34) 34.5(2) C(33) Zr(2) C(35) 35.5(2) C(33) Zr(2) C(36) 33.2(2) C(34) Zr(2) C(35) 59.4(2) C(34) Zr(2) C(36) 57.7(2) C(35) Zr(2) C(36) 58.7(2) C(55) N(1) C(56) 109.0(7) C(55) N(1) C(57) 110.4(7) C(55) N(1)- Li(1) 111.0(6) C(56) N(1) C(57) 107.9(6) C(56) N(1) Li(1) 115.1(6) C(57) N(1) Li(1) 103.2(6) C(58) N(2) C(59) 112.4(7) C(58) N(2) C(60) 111.1(7) C(58) N(2) Li(1) 99.5(6) C(59) N(2) C(60) 104.7(7) C(59) N(2) Li(1) 116.2(6) C(60) N(2) Li(1) 113.1(7) C(61) N(3) C(62) 107.0(7) C(61) N(3) C(63) 108.3(7) C(61) N(3) Li(1) 117.8(6) C(62) N(3) C(63) 110.7(6) C(62) N(3) Li(1) 110.9(6) C(63) N(3) Li(1) 102.0(6) C(64) N(4) C(65) 107.3(7) C(64) N(4) C(66) 112.9(7) C(64) N(4) Li(1) 100.2(5) C(65) N(4) C(66) 109.1(7) C(65) N(4) Li(1) 120.8(6) C(66) N(4) Li(1) 106.4(6) C(67) N(5) C(68) 104.0(10) C(67) N(5) C(69) 109(1) C(67) N(5) Li(2) 103.5(9) C(68) N(5) C(69) 114(1) C(68) N(5) Li(2) 120.3(8) C(69) N(5) Li(2) 103(1) C(78) N(6) C(79) 110(1) C(78) N(6) C(80) 102(1) C(78) N(6) Li(2) 105(1) C(79) N(6) C(80) 110(1)

22 (G1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 21 Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle C(79) N(6) Li(2) 108.3(8) C(80) N(6) Li(2) 119(1) N(8) N(7) C(70) 166(2) N(8) N(7) C(71) 67(1) N(8) N(7) C(72) 89(1) N(8) N(7) Li(2) 68(1) C(70) N(7) C(71) 109(1) C(70) N(7) C(72) 103(1) C(70) N(7) Li(2) 101(1) C(71) N(7) C(72) 113(1) C(71) N(7) Li(2) 115.7(8) C(72) N(7) Li(2) 111(1) N(7) N(8) C(71) 85(2) N(7) N(8) C(72) 64(1) N(7) N(8) C(73) 125(2) N(7) N(8) Li(2) 92(1) C(71) N(8) C(72) 110(1) C(71) N(8) C(73) 121(1) C(71) N(8) Li(2) 131(1) C(72) N(8) C(73) 62(1) C(72) N(8) Li(2) 111(1) C(73) N(8) Li(2) 99(1) N(10) N(9) C(74) 141(1) N(10) N(9) C(75) 108(2) N(10) N(9) C(76) 73(1) N(10) N(9) C(77) 80(1) N(10) N(9) Li(2) 110(1) C(74) N(9) C(75) 32(2) C(74) N(9) C(76) 91(1) C(74) N(9) C(77) 99(1) C(74) N(9) Li(2) 107.6(9) C(75) N(9) C(76) 81(2) C(75) N(9) C(77) 93(2) C(75) N(9) Li(2) 139(2) C(76) N(9) C(77) 149(1) C(76) N(9) Li(2) 106(1) C(77) N(9) Li(2) 97.6(8) N(9) N(10) C(75) 23(1) N(9) N(10) C(76) 58(1) C(75) N(10) C(76) 55(1) Zr(1) C(1) C(2) 74.5(5) Zr(1) C(1) C(5) 73.9(4) C(2) C(1) C(5) 107.0(8) Zr(1) C(2) C(1) 73.9(5) Zr(1) C(2) C(3) 74.5(5) C(1) C(2) C(3) 108.3(8) Zr(1) C(3) C(2) 74.2(5) Zr(1) C(3) C(4) 75.1(5)

23 (G1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 22 Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle C(2) C(3) C(4) 110.0(8) Zr(1) C(4) C(3) 74.0(4) Zr(1) C(4) C(5) 73.3(4) C(3) C(4) C(5) 107.8(8) Zr(1) C(5) C(1) 73.5(4) Zr(1) C(5) C(4) 74.8(4) C(1) C(5) C(4) 106.9(8) Zr(1) C(6) C(7) 76.2(4) Zr(1) C(6) C(8) 77.6(4) Zr(1) C(6) C(9) 84.4(4) C(7) C(6) C(8) 114.4(6) C(7) C(6) C(9) 118.8(6) C(8) C(6) C(9) 116.9(6) Zr(1) C(7) C(6) 68.6(3) Zr(1) C(7) C(10) 124.5(5) C(6) C(7) C(10) 127.1(6) Zr(1) C(8) C(6) 67.4(4) Zr(1) C(8) C(16) 125.8(4) C(6) C(8) C(16) 125.9(6) Zr(1) C(9) C(6) 62.9(3) Zr(1) C(9) C(22) 122.3(4) C(6) C(9) C(22) 126.8(6) C(7) C(10) C(11) 125.8(6) C(7) C(10) C(15) 117.1(6) C(11) C(10) C(15) 116.9(6) C(10) C(11) C(12) 120.0(7) C(11) C(12) C(13) 121.6(7) 0(12) C(13) C(14) 119.2(7) C(13) C(14) C(15) 120.9(8) C(10) C(15) C(14) 121.4(7) C(8) C(16) C(17) 126.1(7) C(8) C(16) C(21) 117.2(6) C(17) C(16) C(21) 116.5(7) C(16) C(17) C(18) 121.1(7) C(17) C(18) C(19) 120.6(8) C(18) C(19) C(20) 120.2(8) C(19) C(20) C(21) 119.2(8) C(16) C(21) C(20) 122.4(8) C(9) C(22) C(23) 124.5(6) C(9) C(22) C(27) 118.5(7) C(23) C(22) 0(27) 116.9(7) C(22) C(23) C(24) 120.8(7) C(23) C(24) C(25) 121.4(9) C(24) C(25) C(26) 119.1(8) C(25) C(26) C(27) 119.3(8) C(22) C(27) C(26) 122.4(8) Zr(2) C(28) C(29) 74.2(5) Zr(2) C(28) C(32) 73.2(5)

24 (G1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 23 Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle C(29) C(28) C(32) 107.9(9) Zr(2) C(29) C(28) 73.6(5) Zr(2) C(29) C(30) 73.8(5) C(28) C(29) C(30) 106.5(8) Zr(2) C(30) C(29) 75.2(5) Zr(2) C(30) C(31) 74.4(5) C(29) C(30) C(31) 110.2(9) Zr(2) C(31) C(30) 74.1(5) Zr(2) C(31) C(32) 73.3(5) C(30) C(31) C(32) 107.6(9) Zr(2) C(32) C(28) 75.1(5) Zr(2) C(32) C(31) 74.9(5) C(28) C(32) C(31) 107.8(9) Zr(2) C(33) C(34) 77.5(4) Zr(2) C(33) C(35) 77.4(3) Zr(2) C(33) C(36) 81.3(4) C(34) C(33) C(35) 114.9(5) C(34) C(33) C(36) 116.7(6) C(35) C(33) C(36) 117.3(6) Zr(2) C(34) C(33) 68.0(3) Zr(2) C(34) C(37) 124.6(4) C(33) C(34) C(37) 124.8(5) Zr(2) C(35) 0(33) 67.1(3) Zr(2) C(35) C(43) 123.6(4) 0(33) C(35) C(43) 126.9(6) Zr(2) C(36) C(33) 65.5(3) Zr(2) C(36) C(49) 123.9(4) C(33) C(36) C(49) 129.2(6) C(34) C(37) C(38) 119.8(6) C(34) C(37) C(42) 124.1(6) C(38) C(37) C(42) 115.9(6) C(37) C(38) C(39) 119.9(7) C(38) C(39) C(40) 123.0(7) 0(39) C(40) C(41) 116.7(7) C(40) C(41) C(42) 121.8(7) C(37) C(42) C(41) 122.7(7) C(35) C(43) C(44) 124.5(6) C(35) 0(43) C(48) 118.5(6) C(44) C(43) C(48) 116.9(6) C(43) C(44) C(45) 118.3(7) C(44) C(45) C(46) 123.5(8) C(45) C(46) C(47) 118.0(7) C(46) C(47) C(48) 121.5(7) C(43) C(48) C(47) 121.8(7) C(36) C(49) C(50) 118.4(6) C(36) C(49) C(54) 124.9(6) C(50) 0(49) C(54) 116.5(6) C(49) C(50) C(51) 121.6(7)

25 V I VV / American fiemical society J. Am. Uhem. soc. VI IV Fage.4.5 Rocriguez bupplemental Page 24 Bond Angles(') (continued) atom atom atom angle atom atom atom angle C(50) C(51) C(52) 119.2(7) C(51) C(52) C(53) 120.6(7) C(52) C(53) C(54) 121.2(7) C(49) C(54) C(53) 120.9(7) N(1) C(57) C(58) 110.1(7) N(2) C(58) C(57) 112.2(7) N(3) C(63) C(64) 111.3(6) N(4) C(64) C(63) 111.3(6) N(5) C(69) C(70) 114(1) N(7) C(70) C(69) 125(1) N(7) C(71) N(8) 27.0(8) N(7) C(72) N(8) 26.2(8) N(7) C(72) C(73) 83(1) N(8) C(72) C(73) 57(1) N(8) C(73) C(72) 59(1) N(8) C(73) C(74) 128(2) C(72) C(73) C(74) 129(2) N(9) C(74) C(73) 101(1) N(9) C(74) C(75) 20(1) C(73) C(74) C(75) 121(2) N(9) C(75) N(10) 47(2) N(9) C(75) C(74) 127(3) N(9) C(75) C(76) 71(2) N(10) C(75) C(74) 173(2) N(10) C(75) C(76) 62(1) C(74) C(75) 0(76) 114(2) N(9) C(76) N(10) 48(1) N(9) C(76) C(75) 27(1) N(10) 0(76) C(75) 62(1) N(9) C(77) C(78) 108(1) N(6) C(78) C(77) 107(1) C(82) C(81) C(87) 43(1) C(81) C(82) C(83) 153(2) 0(81) C(82) C(87) 72(1) C(83) C(82) C(87) 81(1) C(82) C(83) C(84) 164(2) C(82) C(83) C(87) 47(1) C(84) C(83) C(87) 122(2) C(83) C(84) C(85) 103(2) C(84) C(85) C(86) 114(1) C(85) C(86) C(87) 94(1) C(81) C(87) C(82) 64(1) C(81) C(87) C(83) 115(1) C(81) C(87) C(86) 140(1) C(82) C(87) C(83) 50(1) C(82) C(87) C(86) 155(1) C(83) C(87) C(86) 104(1) N(1) Li(1) N(2) 87.9(5)

26 (G1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 25 Bond Angles(') (continued) atom atom atom angle atom atom atom angle N(1) Li(1) N(3) 122.2(7) N(1) Li(1) N(4) 117.1(6) N(2) Li(1) N(3) 119.5(6) N(2) Li(1) N(4) 125.5(7) N(3) Li(1) N(4) 88.6(5) N(5) Li(2) N(6) 107.5(7) N(5) Li(2) N(7) 92.9(6) N(5) Li(2) N(8) 111.7(8) N(5) Li(2) N(9) 121.2(7) N(6) Li(2) N(7) 127.1(8) N(6) Li(2) N(8) 117.7(8) N(6) Li(2) N(9) 95.7(6) N(7) Li(2) N(8) 18.9(5) N(7) Li(2) N(9) 114.7(7) N(8) Li(2) N(9) 102.7(8)

27 V I VV9/ American fiemical society J. Am. uhem. soc. VI I VPage.54.5 Rocriguez bupplemental Page 26 Bond Angles( 0 ) atom atom atom angle atom atom atom angle Zr(1) C(1) H(1) C(2) C(1) H(1) C(5) C(1) H(1) Zr(1) C(2) H(2) C(1) C(2) H(2) C(3) C(2) H(2) Zr(1) C(3) H(3) C(2) C(3) H(3) C(4) C(3) 11(3) Zr(1) C(4) H(4) C(3) C(4) 11(4) C(5) C(4) H(4) Zr(1) C(5) 11(5) C(1) C(5) H(5) C(4) C(5) H(5) Zr(1) C(7) H(22) C(6) C(7 H(22) C(10) C(7) H(22) Zr(1) C(8) 11(23) C(6) C(8) H(23) C(16) C(8) H(23) Zr(1) C(9) H(21) 86.8 C(6) C(9) H(21) C(22) C(9) H(21) C(10) C(11) H(6) C(12) C(11) H(6) C(11) C(12) H(7) C(13) C(12) H(7) C(12) C(13) H(8) C(14) C(13) H(8) C(13) C(14) H(9) C(15) C(14) H(9) C(10) C(15) H(10) C(14) C(15) H(10) C(16) C(17) H(11) C(18) C(17) H(11) C(17) C(18) H(12) C(19) C(18) H(12) C(18) C(19) H(13) C(20) C(19) H(13) C(19) C(20) H(14) C(21) C(20) H(14) C(16) C(21) 11(15) C(20) C(21) H(15) C(22) C(23) H(20) C(24) C(23) H(20) C(23) C(24) H(19) C(25) C(24) H(19) 119.1

28 (G1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 27 Bond Angles(o) (continued) atom atom atom angle atom atom atom angle C(24) C(25) H(18) C(26) C(25) H(18) C(25) C(26) H(17) C(27) C(26) H(17) C(22) C(27) H(16) C(26) C(27) H(16) Zr(2) C(28) H(28) C(29) C(28) H(28) C(32) C(28) H(28) Zr(2) C(29) H(24) C(28) C(29) H(24) C(30) C(29) H(24) Zr(2) C(30) H(25) C(29) C(30) H(25) C(31) C(30) H(25) Zr(2) C(31) H(26) C(30) C(31) H(26) C(32) C(31) H(26) Zr(2) C(32) H(27) C(28) C(32) H(27) C(31) C(32) H(27) Zr(2) C(34) H(44) 99.2 C(33) C(34) H(44) C(37) C(34) H(44) Zr(2) C(35) H(45) 99.8 C(33) C(35) H(45) (43) C(35) H(45) Zr(2) C(36) H(46) 96.5 C(33) C(36) H(46) C(49) C(36) H(46) C(37) C(38) H(29) C(39) C(38) H(29) C(38) C(39) H(30) C(40) C(39) H(30) C(39) C(40) H(31) C(41) C(40) H(31) C(40) C(41) H(32) C(42) C(41) H(32) C(37) C(42) H(33) (41) C(42) H(33) C(43) 0(44) H(34) C(45) C(44) H(34) C(44) C(45) H(35) C(46) C(45) H(35) C(45) C(46) H(36) (47) C(46) H(36) C(46) C(47) H(37) (48) C(47) H(37) 122.6

29 v i/ american onemicai 3ociety J. Am. Linem. 3oc. vi i!) rage-,, i-oariguez 3uppiemental rage L6 Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle C(43) C(48) H(38) C(47) C(48) H(38) C(49) C(50) H(39) C(51) C(50) H(39) C(50) C(51) H(40) C(52) C(51) H(40) C(51) C(52) H(41) C(53) C(52) H(41) C(52) C(53) H(42) C(54) C(53) H(42) C(49) C(54) H(43) C(53) C(54) H(43) N(1) 0(55) H(50) N(1) C(56) H(47) N(1) C(56) H(48) N(1) C(56) H(49) H(47) C(5) H(48) H(47) C(56) H(49) H(48) C(56) H(49) N(1) C(57) H(51) N(1) C(57) H(52) C(58) C(57) H(51) C(58) C(57) H(52) H(51) C(57) H(52) N(2) C(58) H(53) N(2) C(58) H(54) C(57) C(58) H(53) C(57) C(58) H(54) H(53) C(58) H(54) N(2) C(59) H(55) N(2) C(59) H(56) N(2) C(59) H(57) H(55) C(59) H(56) H(55) C(59) H(57) H(56) C(59) H(57) N(2) C(60) H(58) N(2) C(60) H(59) N(2) C(60) H(60) H(58) C(60) H(59) H(58) C(60) H(60) H(59) 0(60) H(60) N(3) C(61) H(61) N(3) C(61) H(62) N(3) C(61) H(63) H(61) C(61) H(62) H(61) C(61) H(63) H(62) C(61) H(63) N(3) C(62) H 109.3

30 v i/ american onemicai 3ociety J. Am. Linem. 3oc. vi i!) rage-,, i-oariguez 3uppiemental rage /-! Bond Angles( 0 ) (continued) atom atom atom angle atom atom atom angle N(3) C(62) H(67) N(3) C(62) H(68) H C(62) H(67) H C(62) H(68) H(67) C(62) H(68) N(3) C(63) H N(3) C(63) H(69) C(64) C(63) H C(64) C(63) H(69) H C(63) H(69) N(4) C(64) H(70) N(4) C(64) H(71) C(63) C(64) H(70) C(63) C(64) H(71) H(70) C(64) H(71) N(4) C(65) H(72) N(4) C(65) H(73) N(4) C(65) H(74) H(72) C(65) H(73) H(72) C(65) H(74) H(73) C(65) H(74) N(4) C(66) H(64) N(4) C(66) H(65) N(4) C(66) H(66) H(64) C(66) H(65) H(64) C(66) H(66) H(65) C(66) H(66) 111.0

31 /YY'"i-U11u1Rd %111rIIud 1 3uuArL J. I-u11. k1~1.3uu. V I I:; ragrj-tj IXAU11gUrL OUPPRI11U1Ld1 f-dgr,.1 Anisotropic Displacement Parameters atom U 11 U 2 2 U 3 3 U 1 2 U 13 U 2 3 Zr(1) (3) (4) (3) (3) (3) (3) Zr(2) (4) (4) (4) (3) (3) (3) Cl(1) 0.052(1) 0.074(1) 0.056(1) (10) (8) (10) C1(2) 0.055(1) 0.046(1) 0.052(1) (9) (9) (9) CI(3) 0.068(1) 0.038(1) 0.061(1) (9) (10) (9) C(4) 0.048(1) 0.060(1) 0.073(1) (9) (9) 0.008(1) N(1) 0.051(4) 0.074(5) 0.060(4) 0.001(3) 0.014(3) 0.007(4) N(2) 0.069(5) 0.059(5) (5) 0.003(4) (4) 0.001(4) N(3) (4) 0.050(4) 0.066(4) (3) 0.020(3) (3) N(4) 0.050(4) 0.042(4) 0.067(4) 0.001(3) 0.020(3) (3) C(1) 0.073(6) 0.119(8) 0.030(4) (6) (4) 0.011(5) C(2) 0.071(6) 0.112(8) 0.042(5) 0.023(6) (4) (5) C(3) 0.086(6) 0.054(6) 0.055(5) (5) (5) (4) C(4) 0.030(4) 0.112(8) 0.047(5) (4) 0.000(3) (5) C(5) 0.087(6) 0.056(5) 0.042(5) 0.025(5) (4) (4) C(6) 0.038(4) 0.045(4) 0.032(4) (3) 0.011(3) (3) C(7) 0.052(4) 0.039(4) 0.043(4) (3) 0.022(3) (3) C(8) 0.043(4) 0.043(4) 0.035(4) (3) 0.009(3) (3) 0(9) 0.047(4) 0.037(4) 0.042(4) (3) 0.016(3) (3) C(10) 0.038(4) 0.049(5) 0.050(4) (3) 0.021(3) (4) C(11) 0.043(4) 0.054(5) 0.074(5) (4) 0.021(4) (4) C(12) 0.045(5) 0.075(6) 0.093(6) (4) 0.024(4) 0.009(5) C(13) 0.061(5) 0.064(6) 0.119(7) 0.000(4) 0.060(4) (5) C(14) 0.074(5) 0.077(6) 0.096(6) (5) 0.055(4) (5)

32 (G1997 American Chemical Society J. Am. Chem. Soc. V 119 Page343 Rodriguez Supplemental Page 31 Anisotropic Displacement Parameters (continued) atom U U 3 3 U1 2 U1 3 U 23 C(15) 0.048(4) 0.081(6) 0.058(4) (4) 0.032(3) (4) C(16) 0.059(5) 0.036(4) 0.041(4) (4) 0.011(3) (3) C(17) 0.065(5) 0.046(5) 0.067(5) (4) 0.017(4) 0.001(4) C(18) 0.090(6) 0.053(5) 0.064(5) (5) 0.027(4) 0.001(4) C(19) 0.120(7) 0.043(5) 0.053(5) (5) 0.021(5) (4) C(20) 0.098(6) 0.040(5) 0.060(5) 0.020(4) 0.028(4) 0.007(4) C(21) 0.091(6) 0.049(5) 0.050(4) 0.007(4) 0.030(4) (4) C(22) 0.031(4) 0.057(5) 0.032(4) (3) 0.005(3) (3) C(23) 0.053(4) 0.057(5) 0.051(4) (4) 0.013(4) (4) C(24) 0.071(6) 0.088(7) 0.063(5) (5) 0.018(4) (5) C(25) 0.058(5) 0.138(9) 0.048(5) (5) 0.024(4) (5) C(26) 0.069(5) 0.112(8) 0.042(5) (5) 0.017(4) 0.002(5) C(27) 0.057(5) 0.077(6) 0.038(4) (4) 0.011(3) (4) C(28) 0.058(5) 0.132(9) 0.039(5) 0.000(6) (4) (5) C(29) 0.126(9) 0.047(6) 0.068(6) 0.018(6) (6) (5) C(30) 0.077(6) 0.094(8) 0.067(6) (5) (5) 0.015(6) C(31) 0.049(5) 0.119(8) 0.062(6) 0.024(5) (5) (6) C(32) 0.094(7) 0.066(6) 0.050(5) (6) (5) 0.006(5) C(33) 0.038(4) 0.037(4) 0.035(4) (3) 0.009(3) (3) C(34) 0.039(4) 0.037(4) 0.034(4) (3) 0.008(3) (3) C(35) 0.043(4) 0.038(4) 0.029(3) (3) 0.009(3) (3) C(36) 0.031(3) 0.038(4) 0.037(4) 0.003(3) 0.012(3) (3) C(37) 0.042(4) 0.035(4) 0.041(4) (3) 0.016(3) (3) C(38) 0.059(5) 0.056(5) 0.067(5) (4) 0.028(4) (4)

33 CIVV/ American fiemical society J. Am. Uhem. soc. VI I Page.54.5 Rocriguez bupplemental vage.2 Anisotropic Displacement Parameters (continued) atom U 11 U2 2 U 33 U 12 U 13 U 2 3 C(39) 0.085(5) 0.056(5) 0.132(6) (4) 0.079(4) (5) C(40) 0.044(4) 0.057(5) 0.116(6) (4) 0.046(4) (5) C(41) 0.040(4) 0.078(6) 0.071(5) 0.004(4) 0.021(4) 0.012(5) C(42) 0.056(5) 0.056(5) 0.054(4) 0.000(4) 0.026(4) (4) C(43) 0.054(4) 0.041(4) 0.030(4) (3) 0.014(3) (3) C(44) 0.069(5) 0.042(5) 0.063(5) (4) 0.028(4) (4) C(45) 0.127(7) 0.037(5) 0.056(5) (5) 0.048(4) 0.003(4) C(46) 0.078(6) 0.049(5) 0.052(5) 0.015(4) 0.016(4) 0.009(4) C(47) 0.070(5) 0.044(5) 0.060(5) 0.019(4) 0.008(4) 0.005(4) C(48) 0.047(4) 0.045(5) 0.052(4) 0.009(3) 0.013(3) 0.001(4) C(49) 0.023(3) 0.040(4) 0.038(4) (3) 0.002(3) (3) C(50) 0.050(4) 0.061(5) 0.044(4) 0.001(4) 0.014(3) 0.004(4) C(51) 0.063(5) 0.085(6) 0.040(4) (4) 0.018(4) 0.004(4) C(52) 0.057(5) 0.081(6) 0.040(4) 0.002(4) 0.017(3) (4) C(53) 0.055(5) 0.068(6) 0.054(5) 0.000(4) 0.014(4) (4) C(54) 0.049(4) 0.044(5) 0.045(4) (3) 0.009(3) (4) C(55) 0.090(6) 0.084(7) 0.085(6) 0.032(5) 0.026(5) 0.036(5) C(56) 0.076(6) 0.079(7) 0.108(7) (5) 0.043(5) (6) C(57) 0.065(5) 0.084(7) 0.061(5) (5) 0.021(4) (5) C(58) 0.053(5) 0.084(6) 0.074(6) (5) 0.006(4) 0.027(5) C(59) 0.106(8) 0.108(8) 0.075(6) (7) 0.010(6) (6) C(60) 0.083(7) 0.114(9) 0.081(7) 0.006(6) (6) 0.021(6) C(61) 0.136(8) 0.066(6) 0.076(6) (6) 0.031(6) 0.009(5) 0.069(6) 0.091(6) (5) C(62) 0.093(6) 0.043(5) (5)

34 CIVV/ American fiemical society J. Am. Uhem. soc. VI I Page.54.5 Rocriguez bupplemental Page ad Anisotropic Displacement Parameters (continued) atom U1" U22 U 3 3 U 1 2 U 13 U 2 3 C(63) 0.069(5) 0.081(6) 0.084(6) (5) 0.042(4) (5) C(64) 0.053(5) 0.069(6) 0.088(6) (4) 0.021(4) (5) C(65) 0.076(7) 0.101(8) 0.110(8) 0.016(6) 0.002(6) 0.010(7) C(66) 0.083(7) 0.112(9) 0.148(9) 0.004(6) 0.023(6) (7) Li(1) 0.039(6) 0.056(8) 0.063(8) 0.001(6) 0.017(6) 0.006(6) The general temperature factor expression: exp(-2w 2 (a* 2 Uh 2 + b* 2 U 2 2 k 2 + c* a*b*Ul 2 hk + 2a*c*Ulahl + 2b*c*U 2 3kl))

35 CIV9/ American fiemical society J. Am. ulem. soc. VI 11V Fage.54.5 Rocriguez bupplemental Page 34 C84 C83 C82 C81 C87 C85 C86 C57 C58 C60 C30 C61 C45 C46 C64 C63 C41

36 CIV9/ American fiemical society J. Am. ulem. soc. VI 11V Fage.54.5 Rocriguez bupplemental Page 33 C79 C71 3C75 C74 C76 C4 C26 C20 SC19 (" C 14 C12 C13

37 UI99 American Lhemical Society J. Am. Uhem. soc. V I IV Fagei4i Kocriguez bupplemental Fage.5 Solution for 6: Single crystals suitable for a crystallographic diffraction study were grown by slow evaporation of a benzene solution at room temperature (23 *C). An Enraf-Nonius CAD4 diffractometer with XMo Ko graphite monochromated radiation ( A) was used for data collection. The scan type, rate, and range were (o/20, */min and tano, respectively. A take off angle of 2.6 and total background time of (scan time)/2 were employed. A single crystal was mounted on a glass fiber and cell constants determined from 25 carefully centered reflections. Three standard reflections were used to monitor any variation throughout data collection (i.e., decay, etc.). The quadrants of data collected are shown in Table 5 of the paper. The TEXSAN 9 software package from Molecular Structure Corporation was used for data reduction and structure solution. The metal was located by Patterson map solution. 10 Expansion of the structures with DIRDIF 2 revealed all the non-hydrogen atoms. Isotropic refinement was followed with an absorption correction using the program DIFABS. 1 1 Anisotropic refinement was performed using full-matrix least-squares 3 for the indicated atoms (see below for details). Hydrogen atoms were placed in idealized position before the final refinements was carried out to convergence. The low datalvariable ratio in the data sets for [Li(TMEDA)2][Cp*(DBM)ZrC2] did not allow anisotropic refinement of all non-hydrogen atoms. 10 SAPI91: Fan, H.-F Structure Analysis Programs with Intelligent Control, Rigaku Corporation, Tokyo, Japan. 11 DIFABS: Walker, N.; Stuart, G Act. Cryst. 1983, A39, 158. An empirical absorption correction program.

38 VI99I American fiemical Society J. Am. lem. soc. V II Fagei4i Roclriguez bupplementa ipage.i Summary of Crystalographic Data for [Cp*(DBM)ZrCl 2 ][Li(TMEDA)2] empirical formula color formula weight, amu crystal size, mm cryst syst space group z a, A b, A c, A V, A 3 dcalc, g/cm 3 T, 'C scan type reflections collected unique reflections -agreement of equivalent data (Rin) no. of observations (I >3.00a(I)) no. of parameters varied abs coeff, cm- 1 p-factor abs correction radiation 20 range of transm factors Ra; Rob max Shift/error in final cycle goodness of fitc largest hole and peak in final E map ZrC38H61Cl2LiN4 burgundy x 0.38 x 0.23 orthorhombic Pbca (No.61) (1) 33.85(2) (6) 8226(13) o/ differential MoKa (X = A) 38.0' ; ; 51 ar = X(IFol - IFcI)/TIFoI. br 03 = [La 3 (IFoI - IFCI) 2 /LcOlFoI 2 I1/2 cs = goodness of fit = (X(IFol - IFcl)/a)/(n-m), where n is the number of reflections used in the refinement and m is the number of variables

39 CIV9/ American fiemical society J. Am. Ulem. soc. VI 11V Fage.54.5 Rocriguez bupplemental Page da Positional Parameters and Bq for Compound [Cp*Zr(DBMM)CI 2 1[Li(TMEDA) 2 1* Atom x y z B (A2) Zr (2) (6) (1) 2.4(1) Cl(1) (5) (2) (4) 4.2(4) C1(2) (4) (2) (4) 4.1(4) N(1) 0.851(1) (7) 0.866(1) 4.8(6) N(2) 0.655(1) (6) 0.898(1) 3(1) N(3) 0.680(2) (6) 0.878(1) 4(1) N(4) 0.730(1) (6) 1.037(1) 4(1) C(1) 0.218(2) (7) 0.086(2) 2.0(7) C(2) 0.147(2) (7) 0.025(2) 2.8(6) C(3) 0.186(2) (7) (2) 3.1(7) C(4) 0.283(2) (7) (2) 2.9(7) C(5) 0.301(2) (7) 0.049(2) 3(2) C(6) 0.199(2) (7) 0.171(2) 4(2) C(7) 0.045(2) (7) 0.044(2) 5(2) C(8) 0.135(2) (8) (2) 4(2) C(9) 0.350(2) (8) (2) 4.1(8) C(10) 0.393(2) (8) 0.092(2) 3.7(7) C(11) 0.225(1) (6) 0.063(1) 1.4(6) C(12) 0.134(1) (6) 0.052(1) 1.6(5) C(13) 0.281(1) (6) 0.119(1) 1.8(6) C(14) 0.272(1) (5) 0.003(1) 1.8(5) C(15) 0.374(2) (8) 0.154(1) 2.8(6) C(16) 0.427(2) (7) 0.133(1) 3(2) C(17) 0.511(2) (8) 0.177(2) 4(2)

40 CIV9/ American fiemical society J. Am. ulem. soc. VI I Fage.54.5 Rocriguez bupplemental Page dj C(18) 0.547(2) (8) 0.237(2) 4(2) C(19) 0.491(2) (8) 0.259(2) 4(2) C(20) 0.404(2) (7) 0.214(1) 3(2) C(21) 0.227(2) (7) (1) 2.7(6) C(22) 0.282(1) (6) (1) 3(1) C(23) 0.244(2) (6) (1) 3.3(5) C(24) 0.158(2) (7) (1) 3.1(6) C(25) 0.100(2) (7) (2) 4(2) C(26) 0.134(2) (7) (1) 3(1) C(27) 0.736(2) (7) 0.878(1) 4.3(7) C(28) 0.809(2) (8) 0.828(2) 7(2) C(29) 0.604(2) (6) 0.969(1) 3.0(6) C(30) 0.591(2) (7) 0.828(2) 4.1(7) C(31) 0.916(2) (9) 0.931(2) 6.8(9) C(32) 0.904(2) (9) 0.803(2) 7.0(9) C(33) 0.659(2) (9) 0.952(2) 7(2) C(34) 0.719(2) (8) 1.017(2) 7(2) C(35) 0.598(2) (7) 0.825(1) 3.8(7) C(36) 0.766(2) (7) 0.830(2) 5(2) C(37) 0.650(2) 0.128(1) 1.086(2) 8(2) C(38) 0.820(2) 0.140(1) 1.085(2) 6(2) Li 0.727(3) 0.117(1) 0.917(2) 4(1) H(1) H(2) H(3) H(4) H(5)

41 V I VV9/ American fiemical society J. Am. ulem. soc. VI I Fage.54.5 Rocriguez bupplemental Page 4u H(6) I H(7) H(8) H(9) H(10) H(11) H(12) H(13) H(14)

J. Med. Chem., 1996, 39(14), , DOI: /jm960098l

J. Med. Chem., 1996, 39(14), , DOI: /jm960098l J. Med. Chem., 1996, 39(14), 2835-2843, DOI:10.1021/jm960098l Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical