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Table 1. Selected bond distances (A) and angles for the hydrido trinuclear clusters [Rh3(µ-H)
(µ3-S)2{P(OPh)3}4(cod)] (1) and [Rh2Ir2(µ-H)(µ3-S)2{P(OPh)3}4(cod)] (4).
1 4 1 4 Rh(1)-Rh(2) 2.9332(5) 3.0843(5) Rh(1)-Rh(3)/Ir 3.0774(5) 2.9480(4) Rh(2)-Rh(3)/Ir 3.0839(5) 3.0298(4) Rh(1)-S(1) 2.3505(11) 2.3502(11) Rh(2)-S(1) 2.3533(10) 2.3463(11) Rh(1)-S(2) 2.3501(11) 2.3481(11) Rh(2)-S(2) 2.3502(12) 2.3406(12) Rh(1)-P(1) 2.1939(11) 2.1835(11) Rh(2)-P(3) 2.1944(12) 2.1824(12) Rh(1)-P(2) 2.2072(12) 2.1993(11) Rh(2)-P(4) 2.1968(11) 2.1866(12) Rh(3)/Ir-S(1) 2.3194(11) 2.3296(10) Rh(3)/Ir-S(2) 2.3188(11) 2.3270(10) Rh(3)/Ir-C(1) 2.163(4) 2.171(4) Rh(3)/Ir-C(5) 2.157(4) 2.166(4) Rh(3)/Ir-C(2) 2.194(4) 2.191(4) Rh(3)/Ir-C(6) 2.185(4) 2.186(4) Rh(3)/Ir-M(1)# 2.064(5) 2.066(5) Rh(3)/Ir-M(2)# 2.057(3) 2.061(3) P(1)-O* 1.617(2) 1.620(2) P(2)-O* 1.610(2) 1.609(2) P(3)-O* 1.610(2) 1.612(2) P(4)-O* 1.617(2) 1.614(2) C(1)-C(2) 1.390(6) 1.398(6) C(5)-C(6) 1.388(6) 1.399(6) S(1)-Rh(1)-S(2) 82.60(4) 83.21(4) S(1)-Rh(2)-S(2) 82.53(4) 83.46(4) S(1)-Rh(1)-P(1) 94.63(4) 94.43(4) S(1)-Rh(2)-P(3) 90.30(4) 90.22(4) S(1)-Rh(1)-P(2) 172.62(4) 173.10(4) S(1)-Rh(2)-P(4) 177.83(5) 177.68(4) S(2)-Rh(1)-P(1) 177.22(4) 175.81(4) S(2)-Rh(2)-P(3) 172.59(4) 173.68(4) S(2)-Rh(1)-P(2) 90.24(4) 89.94(4) S(2)-Rh(2)-P(4) 95.36(5) 94.64(4) P(1)-Rh(1)-P(2) 92.53(4) 92.36(4) P(3)-Rh(2)-P(4) 91.79(5) 91.67(5)
S(1)-Rh(3)/Ir-S(2) 83.96(4) 84.13(4) M(1)-Rh(3)/Ir-M(2)# 86.57(14) 86.04(14) S(1)-Rh(3)/Ir-M(1)# 175.45(12) 177.06(11) S(2)-Rh(3)/Ir-M(1)# 95.24(10) 95.11(10) S(1)-Rh(3)/Ir-M(2)# 94.61(11) 94.95(11) S(2)-Rh(3)/Ir-M(2)# 174.88(10) 175.43(9) Rh(1)-S(1)-Rh(2) 77.16(3) 82.10(3) Rh(1)-S(2)-Rh(2) 77.23(3) 82.27(3) Rh(1)-S(1)-Rh(3)/Ir 82.44(3) 78.09(3) Rh(1)-S(2)-Rh(3)/Ir 82.46(3) 78.18(3) Rh(2)-S(1)-Rh(3)/Ir 82.59(3) 80.78(3) Rh(2)-S(2)-Rh(3)/Ir 82.67(4) 80.95(3) P(1)-O-C* 123.7(2) 123.7(2) P(3)-O-C* 129.1(2) 128.0(2) P(2)-O-C* 128.1(3) 128.2(3) P(4)-O-C* 124.7(2) 124.4(2) C(2)-C(1)-C(8) 125.3(4) 124.7(4) C(4)-C(5)-C(6) 125.7(4) 126.9(4) C(1)-C(2)-C(3) 124.4(5) 123.3(5) C(5)-C(6)-C(7) 123.9(5) 122.6(5)
# M(1) and M(2) represent the midpoints of the coordinated olefinic bonds, C(1)-C(2) and C(5)-C(6). * Mean
Table 2. 1H 2D EXSY-derived rate constants (k1 and k-1/s-1) and activation energies (ΔG1# and ΔG-1#/kJ mol-1) for the equilibrium a D b in trinuclear hydrido-sulfido clusters.[a]
Cluster tm (ms) T1 (ms) k1 (s-1) [b] k-1 (s-1) [b] ΔG1 # [c] (kJ mol-1) ΔG-1# [c] (kJ mol-1) K = k1/ k-1 1 300 750 3.47 2.11 70.4 71.6 1.64 2 300 900 5.52 5.28 69.2 69.3 1.05 3 200 750 2.94 3.06 70.8 70.7 0.96 5 100 440 4.61 9.68 69.7 67.8 0.48 8 300 800 4.30 2.15 69.8 71.6 2.00
[a] 2D-EXSY spectra (500 MHz) were recorded at 300 K using saturated C
6D6 solution of the clusters. [b] The
integrations for the exchange cross-peak were processed using the EXSYCalc program to obtain the rate constants k1 and k-1. [c] Eyring equation was used to calculate activation energies ΔG1# and ΔG-1#; ΔG# = -
Figure and Scheme legends