HYDRIDE TRANSFER REACTIONS OF TRANSITION METAL HYDRIDES IN THE PREPARATION OF [CP(CO)(3)W(ETA(1)-ALDEHYDE)]+OTF- AND [CP(CO)(3)W(ETA(1)-KETONE)]+OTF- COMPLEXES

摘要

The reaction of Ph(C=O)Cl with Cp(CO)(3)WH and HOTf gives the eta(1)-aldehyde complex [Cp(CO)(3)W eta(1)-PhCHO)] +OTf-. The structure of [Cp(CO)(3)W(eta(1) -PhCHO)] +OTf- (C16H11F3O7SW) was determined by single crystal X-ray diffraction (triclinic, space group P (1) over bar, a = 10.639(5), b = 10.752(4), c = 10.096(3) Angstrom, a = 91.38(3), beta 117.08(3), gamma = 66.01(4)degrees, Z = 2). Decomposition of this compound in CH2Cl2 solution follows first-order kinetics (k = 3.6(2) X 10(-4) s(-1) at 25 degrees C) and produces free PhCHO and Cp(CO)(3)WOTf. The eta(1)-CH3CHO complex [Cp(CO)(3)W(eta(1)-CH3CHO)]+OTf- was similarly prepared from the reaction of acetyl chloride with Cp(CO),WH and HOTf. Hydrogenation of alpha,beta-unsaturated aldehydes by Cp(CO)(3)WH and HOTf produces [Cp(CO)(3)W(eta 1-RCHO)]+OTf- complexes that were isolated and fully characterized; analogous reactions with alpha,beta-unsaturated ketones gives [Cp(CO)(3)W(eta(1)-O = CRR')]+OTf- complexes. All of these aldehyde and ketone complexes with OTf- release free aldehyde or ketone in solution and produce Cp(CO)(3) WOTf, but[Cp(CO)(3)W(eta(1)-2-butanone)]+BAr'(-)(4) (Ar'=3,5-bis(trifluoromethyl)phenyl) is much more stable. [References: 100]