Synthesis and structure of ketene complexes of permethylzirconocene and their hydrogenation to zirconium enolate hydrides

Abstract

The reduction of carbon monoxide by Cp*/sub 2/ZrH/sub 2/ (1, Cp* = n/sup 5/-C/sub 5/Me/sub 5/) is complex and yields a variety of products depending on reaction conditions. Whereas the mechanism leading to trans-(Cp*/sub 2/ZrH)/sub 2/(..mu..-OCH=CHO) from 1 and free CO is relatively well established, the steps leading to cis-(Cp*/sub 2/ZrH)/sub 2/(..mu..-OCH=CHO) (4) from 1, Cp*/sub 2/Zr(CO)/sub 2/ (2), and H/sub 2/ are largely speculative. The favored scheme involves initial attack of 1 at a carbonyl ligand of 2 followed by carbene-carbonyl coupling affording coordinated ''zirconoxy'' ketene 3, which undergoes hydrogenation to 4. The cis geometry of this enediolate product was proposed to result from (i) the structure of 3 in which the bulky Cp*/sub 2/ZrO moieties are sterically constrained in a cis arrangement and (ii) its stereospecific hydrogenation to 4. Recently a general route to titanocene and zirconocene ketene complexes, dehydrohalogenation of haloacyl compounds, has been developed. Application of this methodology to the permethylzirconocene system has led to isolation of monomeric, Lewis base adducts of Cp*/sub 2/Zr(C,O-n/sup 2/-R/sub 2/C=CO). Here the results of a structure determination for Cp*/sub 2/Zr(py)(C,O-n/sup 2/-H/sub 2/C=CO) (py = pyridine) and the stereochemistry of the hydrogenation of the tert-butyl ketene complex, which bears on themore » proposed CO reduction mechanism are reported.« less