Coordination of alkenes and alkynes to a cationic d(0) zirconocene alkoxide complex.
This paper describes the synthesis of base-free (C5R5)2Zr(OtBu)+ cations, the direct observation of nonchelated alkene and alkyne adducts of these cations, and studies of the thermodynamic and dynamic properties of these novel species. Reaction of %@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%2%@sbx@%%@/hd@%ZrMe%@sb@%2%@sbx@%%@mx@% (Cp' = C5H4Me) with tert-butyl alcohol followed by [Ph3C][B(C6F5)4] in benzene yields [%@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%2%@sbx@%%@/hd@%Zr%@/hd@%%@fn;(;vis;full;auto@%O%@ital@%%@ex@%t%@rsf@%%@exx@%%@/hd@%Bu%@fnx;);vis;full@%%@/hd@%%@mx@% ][B(C6F5)4] (1), which exists as %@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%2%@sbx@%%@/hd@%Zr%@/hd@%%@fn;(;vis;full;auto@%O%@ital@%%@ex@%t%@rsf@%%@exx@%%@/hd@%Bu%@fnx;);vis;full@%%@/hd@%%@fn;(;vis;full;auto@%ClR%@fnx;);vis;full@%%@ex@%+%@exx@%%@mx@% solvent adducts in C6D5Cl and CD2Cl2 solutions. Addition of ligands L (L = ethylene, propylene, propyne, 2-butyne, CO, phenylacetylene, allene, 1-hexene, cis-2-butene) to 1 in CD2Cl2 at -89 degrees C results in reversible formation of %@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%2%@sbx@%%@/hd@%Zr%@/hd@%%@fn;(;vis;full;auto@%O%@ital@%%@ex@%t%@rsf@%%@exx@%%@/hd@%Bu%@fnx;);vis;full@%%@/hd@%%@fn;(;vis;full;auto@%L%@fnx;);vis;full@%%@ex@%+%@exx@%%@mx@% adducts. NMR data for %@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%2%@sbx@%%@/hd@%Zr%@/hd@%%@fn;(;vis;full;auto@%O%@ital@%%@ex@%t%@rsf@%%@exx@%%@/hd@%Bu%@fnx;);vis;full@%%@/hd@%%@fn;(;vis;full;auto@%H%@sb@%2%@sbx@%C=%@/bd@%CHMe%@fnx;);vis;full@%%@ex@%+%@exx@%%@mx@% (4) indicate that the propylene coordinates unsymmetrically and is polarized with positive charge buildup at Cint. Equilibrium constants, defined by Keq = [Zr-L][1]-1[L]-1, vary in the order CO > propyne > 2-butyne > phenylacetylene > ethylene > allene > propylene > 1-hexene > cis-2-butene > vinyl chloride. Loss of L from %@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%2%@sbx@%%@/hd@%Zr%@/hd@%%@fn;(;vis;full;auto@%O%@ital@%%@ex@%t%@rsf@%%@exx@%%@/hd@%Bu%@fnx;);vis;full@%%@/hd@%%@fn;(;vis;full;auto@%L%@fnx;);vis;full@%%@ex@%+%@exx@%%@mx@% to give 1 appears to proceed via associative displacement by CD2Cl2 in most cases.
Stoebenau
Edward J
EJ
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA.
Jordan
Richard F
RF