Addition reactions of Cp*Ru(1-5-η-CH2CHCRCHSO2) (R = H, Me) with carbon monoxide, phosphorus, sulfur and nitrogen ligands: Spectroscopic and structural characterization of Cp*Ru(1-2,5-η-butadienesulfonyl)(L)

Abstract

A series of chiral compounds Cp*Ru(1-2,5-η-butadienesulfonyl)(L) (Cp* = C5Me5; butadienesulfonyl = CH2CHCRCHSO2) were prepared by treating Cp*Ru(1-5-η-CH2CHCRCHSO2) [R = H (1), Me (1Me)] with CO, P(OMe)3, a variety of phosphines, sulfur and nitrogen ligands. All addition reactions were selective, with the exception of PMe3 and P(OMe)3. Even in solution, NMR experiments show a rigid structure for the PPh3 adduct, while PPh2Me adduct shows dynamic behavior. 1H NMR demonstrates the formation and equilibrium reactions for both protio and deuterated adducts of the type Cp*Ru(1-2,5-η-CH2CHCRCHSO2)(L) [R = H, L = CH3CN; R = Me, L = CH3CN, DMSO and Py] in different deuterated solvents, such as C6D6, (CD3)2CO and CD3CN. Addition of deuterated donor ligands into 1 or 1Me occur at faster rate than non-deuterated analogues. X-ray crystal structure data are reported for Cp*Ru(1-2,5-η-CH2CHCRCHSO2)(L) [R = H, L = CO (2), PPh3 (3), PMe3 (6), P(OMe)3 (7), DMSO (8); R = Me, L = PPh3 (3Me), DMSO (8Me), Py (9Me), Py-d5 (9DMe)], as well as the side-product Cp*RuCl(P(CD3)2) (12D).