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 (5-C5H5)Re(NO)(PPh3)(OTf) and sulfides MeSR (R = Me (a), Et (b), i-Pr (c), t-Bu (d)) give sulfide complexes [(6-C5H5)Re(NO)(PPh3)(S(R)Me)]+TfO (2a-d+TfO; 91-51%). Reactions of [(5-C5H5)Re(NO)(PPh3)(ClCH2Cl)]+BF4 with SMe2 and O=SMe2 give 2a+BF4 (64%) and DMSO complex [(5-C5H5)Re(NO)(PPh3)(S(=O)Me2)]+BF4 (4a+BF4; 86%). Reaction of 4a+BF4 and excess SMe2 gives 2a+BF4 (83%). Reactions of (5-C5H5)Re(NO)(CO)(OTf) with SMe2 and S(t-Bu)2 give carbonyl-substituted sulfide complexes [(5-C5H5)Re(NO)(CO)(SR2)]+TfO (6a, e+TfO; 99-81%). Sulfide complexes 2a+TfO and 6a, e+TfO exhibit dynamic NMR behavior (G*(TC) = 9.5-12.9 kcal/mol) arising from inversion of configuration at sulfur. Crystal structures of 2a+TfOCH2Cl2 (monoclinic, P21/n, a = 8.254 (2) , b = 27.429 (8) , c = 13.782 (7) , = 96.67 (3), Z = 4), 4a+BF4 (triclinic, P1, a = 10.472 (1) , b = 14.162 (2) , c = 9.441 (1) , a = 101.036 (3). = 90.891 (3), = 87.781 (3), Z = 4), and 6a+TfO (monoclinic, P21/n, a = 8.346 (2) , b = 25.387 (10) , c = 7.287 (2) , = 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.
