The synthesis and solid-state structures of (mu-3-eta-2-C2-t-Bu)(CO)9Ru3(mu-3-Hg)Ru(eta-5-C5H5)(CO)2 (1), (mu-3-eta-2-t-Bu)(CO)9Ru3(mu-3-Hg)Fe(eta-5-C5H5)(CO)2 (2), (mu-3-eta-2-C2-t-Bu)(CO)9Os3(mu-3-Hg)Mo(eta-5-C5H5)(CO)3 (3), (mu-3-eta-2-C2-t-Bu)(CO)9Os3(mu-3-Hg)Co(CO)4 (4), and [(mu-H)(mu-3-S)(CO)9Os3]2(mu-4-Hg) (6) are reported. The structures are compared to known analogues with regard to their mercury-transition-metal bonds and the general skeletal geometry of the cluster. The solution dynamics of 6 as studied by variable-temperature (VT) H-1 and C-13 NMR spectroscopies are also reported for comparison with the analogous complex [(mu-3-eta-2-C2-t-Bu)(CO)9Ru3]2(mu-4-Hg) (5). Compound 1 crystallizes in the triclinic space group P1BAR with a = 9.339 (1) angstrom, b = 10.773 (2) angstrom, c = 14.666 (4) angstrom, alpha = 96.00 (2)-degrees, beta = 108.00 (2)-degrees, gamma = 91.70 (1)-degrees, V = 1393 (2) angstrom-3, and Z = 2. Least-squares refinement of 3726 observed reflections gave a final R = 0.045 (R(w) = 0.051). Compound 2 crystallizes in the triclinic space group P1BAR with a = 10.710 (1) angstrom, b = 14.639 (3) angstrom, c = 9.310 (3) angstrom, alpha = 107.90 (2)-degrees, beta = 92.65 (2)-degrees, gamma = 96.02 (1)-degrees, V = 1377 (2) angstrom-3, and Z = 2. Least-squares refinement of 3535 observed reflections gave a final R = 0.045 (R(w) = 0.053). Compound 3 crystallizes in the monoclinic space group P2(1)/n with a = 15.890 (4) angstrom, b = 12.629 (3) angstrom, c = 15.299 (3) angstrom, beta = 104.16 (2)-degrees, V = 2977 (2) angstrom-3, and Z = 4. Least-squares refinement of 3301 observed reflections gave a final R = 0.067 (R(w) = 0.072). Compound 4 crystallizes in the orthorhombic space group Pbca with a = 16.574 (5) angstrom, b = 18.251 (5) angstrom, c = 18.445 (5) angstrom, V = 5580 (3) angstrom-3, and Z = 8. Least-squares refinement of 2814 observed reflections gave a final R = 0.049 (R(w) = 0.053). Compound 6 crystallizes in the triclinic space group P1BAR with a = 9.363 (3) angstrom b = 20.814 (3) angstrom, c = 9.030 (2) angstrom, alpha = 91.61 (1)-degrees, beta = 115.82 (2)-degrees, gamma = 95.51 (2)-degrees, V = 1572 (1) angstrom-3, and Z = 2. Least-squares refinement of 3896 observed reflections gave a final R = 0.077 (R(w) = 0.082).
MERCURY-BRIDGED TRANSITION-METAL CLUSTERS .5. SYNTHESIS AND STRUCTURE OF (MU-3-ETA-2-C2-T-BU)(CO)9M3(MU-3-HG)M' [M = RU, OS-M' = FE(ETA-5-C5H5)(CO)2, RU(ETA-5-C5H5)(CO)2, MO(ETA-5-C5H5)(CO)3, CO(CO)4] AND [(MU-H)(MU-3-S)(CO)9OS3]2(MU-4-HG)
GOBETTO, Roberto;
1991-01-01
Abstract
The synthesis and solid-state structures of (mu-3-eta-2-C2-t-Bu)(CO)9Ru3(mu-3-Hg)Ru(eta-5-C5H5)(CO)2 (1), (mu-3-eta-2-t-Bu)(CO)9Ru3(mu-3-Hg)Fe(eta-5-C5H5)(CO)2 (2), (mu-3-eta-2-C2-t-Bu)(CO)9Os3(mu-3-Hg)Mo(eta-5-C5H5)(CO)3 (3), (mu-3-eta-2-C2-t-Bu)(CO)9Os3(mu-3-Hg)Co(CO)4 (4), and [(mu-H)(mu-3-S)(CO)9Os3]2(mu-4-Hg) (6) are reported. The structures are compared to known analogues with regard to their mercury-transition-metal bonds and the general skeletal geometry of the cluster. The solution dynamics of 6 as studied by variable-temperature (VT) H-1 and C-13 NMR spectroscopies are also reported for comparison with the analogous complex [(mu-3-eta-2-C2-t-Bu)(CO)9Ru3]2(mu-4-Hg) (5). Compound 1 crystallizes in the triclinic space group P1BAR with a = 9.339 (1) angstrom, b = 10.773 (2) angstrom, c = 14.666 (4) angstrom, alpha = 96.00 (2)-degrees, beta = 108.00 (2)-degrees, gamma = 91.70 (1)-degrees, V = 1393 (2) angstrom-3, and Z = 2. Least-squares refinement of 3726 observed reflections gave a final R = 0.045 (R(w) = 0.051). Compound 2 crystallizes in the triclinic space group P1BAR with a = 10.710 (1) angstrom, b = 14.639 (3) angstrom, c = 9.310 (3) angstrom, alpha = 107.90 (2)-degrees, beta = 92.65 (2)-degrees, gamma = 96.02 (1)-degrees, V = 1377 (2) angstrom-3, and Z = 2. Least-squares refinement of 3535 observed reflections gave a final R = 0.045 (R(w) = 0.053). Compound 3 crystallizes in the monoclinic space group P2(1)/n with a = 15.890 (4) angstrom, b = 12.629 (3) angstrom, c = 15.299 (3) angstrom, beta = 104.16 (2)-degrees, V = 2977 (2) angstrom-3, and Z = 4. Least-squares refinement of 3301 observed reflections gave a final R = 0.067 (R(w) = 0.072). Compound 4 crystallizes in the orthorhombic space group Pbca with a = 16.574 (5) angstrom, b = 18.251 (5) angstrom, c = 18.445 (5) angstrom, V = 5580 (3) angstrom-3, and Z = 8. Least-squares refinement of 2814 observed reflections gave a final R = 0.049 (R(w) = 0.053). Compound 6 crystallizes in the triclinic space group P1BAR with a = 9.363 (3) angstrom b = 20.814 (3) angstrom, c = 9.030 (2) angstrom, alpha = 91.61 (1)-degrees, beta = 115.82 (2)-degrees, gamma = 95.51 (2)-degrees, V = 1572 (1) angstrom-3, and Z = 2. Least-squares refinement of 3896 observed reflections gave a final R = 0.077 (R(w) = 0.082).
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