Synthesis, structure, and dynamic behavior of rhenium sulfide and sulfoxide complexes of the formula [(.eta.5-C5H5)Re(NO)(L)(XRR')]+X'- (X = S, SO)
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Reactions of (η5-C5H5)Re(NO)(PPh3)(OTf) and sulfides MeSR (R = Me (a), Et (b), i-Pr (c), t-Bu (d)) give sulfide complexes [(η6-C5H5)Re(NO)(PPh3)(S(R)Me)]+TfO− (2a-d+TfO−; 91-51%). Reactions of [(η5-C5H5)Re(NO)(PPh3)(ClCH2Cl)]+BF4− with SMe2 and O=SMe2 give 2a+BF4− (64%) and DMSO complex [(η5-C5H5)Re(NO)(PPh3)(S(=O)Me2)]+BF4− (4a+BF4−; 86%). Reaction of 4a+BF4− and excess SMe2 gives 2a+BF4− (83%). Reactions of (η5-C5H5)Re(NO)(CO)(OTf) with SMe2 and S(t-Bu)2 give carbonyl-substituted sulfide complexes [(η5-C5H5)Re(NO)(CO)(SR2)]+TfO− (6a, e+TfO−; 99-81%). Sulfide complexes 2a+TfO− and 6a, e+TfO− exhibit dynamic NMR behavior (ΔG*(TC) = 9.5-12.9 kcal/mol) arising from inversion of configuration at sulfur. Crystal structures of 2a+TfO−•CH2Cl2 (monoclinic, P21/n, a = 8.254 (2) Å, b = 27.429 (8) Å, c = 13.782 (7) Å, ß = 96.67 (3)°, Z = 4), 4a+BF4− (triclinic, P1, a = 10.472 (1) Å, b = 14.162 (2) Å, c = 9.441 (1) Å, a = 101.036 (3)°. ß = 90.891 (3)°, γ = 87.781 (3), Z = 4), and 6a+TfO− (monoclinic, P21/n, a = 8.346 (2) Å, b = 25.387 (10) Å, c = 7.287 (2) Å, ß = 96.95 (3)°, Z = 4) are reported. The sulfoxide oxygen in 4a+BF4− is syn to the PPh3 ligand (torsion angle P-Re-S-O = 17°). © 1991, American Chemical Society. All rights reserved.
author list (cited authors)
Quiros Mendez, N., Arif, A. M., & Gladysz, J. A.