Physical Organic Chemistry of Transition Metal Carbene Complexes. 18.1 Kinetics of Reversible Cyclization of the Fischer Carbene Complexes (CO)5MC(SCH2CH2OH)Ph and (CO)5MC(OCH2CH2OH)Ph (M = Cr, W) in Aqueous Acetonitrile

Abstract

Rate and equilibrium constants for the conversion of (CO)5CrC(OCH2CH2OH)Ph (8-CrOOH), (CO)5WC(OCH2CH2OH)Ph (8-WOOH), (CO)5CrC(SCH2CH2OH)Ph (8-CrSOH), and (CO)5WC(SCH2CH2OH)Ph (8-WSOH) into the corresponding cyclic adducts (9-CrOO- for M = Cr, X = O; 9-WOO- for M = W, X = O; 9-CrSO- for M = Cr, X = S; 9-WSO- for M = W, X = S) are reported. Under basic conditions the reaction occurs via the respective oxyanions, (CO)5CrC(OCH2CH2O-)Ph (8-CrOO-), etc.; under acidic conditions the reaction may either be concerted with water acting as a general base catalyst or stepwise via a zwitterionic intermediate. The absence of buffer catalysis suggests but does not prove the operation of the stepwise mechanism. The equilibrium constants for cyclization of 8-CrSO- and 8-WSO- are about 1 order of magnitude higher than for 8-CrOO- and 8-WOO-, respectively. For the rate constants the situation is reversed, with 8-CrOO- and 8-WOO- being substantially more reactive than 8-CrSO- and 8-WSO-, respectively. These results reflect t...