Hydrosilylation catalysis by C-2-Symmetric bis(silylamido) complexes of yttrium

The yttrium hydride {[DADMB]YH(THF)}(2) (2; DADMB = 2,2'-bis(tert-butyldime thylsilylamido)-6, 6'-dimethylbiphenyl), conveniently generated in situ fro m [DADMB]YMe(THF)(2) (1), is an active olefin hydrosilylation catalyst. Thi s system represents the first use of a d(o) metal complex with non-Cp ligan ds in the catalytic hydrosilylation of olefins. Studies of the reactivity a nd regio- and enantioselectivity for various olefins and silanes are presen ted. High preference for terminal addition in the case of aliphatic olefins is observed, while aromatic olefins exhibit preference for 2,1-addition. B oth primary and secondary silanes have been employed. Preliminary studies o f the enantioselectivity of the chiral catalyst show that 90% ee can be ach ieved in the hydrosilylation of norbornene with PhSiH3. Kinetic studies sup port a mechanism consistent with the generally accepted one for hydrosilyla tion catalyzed by early transition metal species, involving rapid olefin in sertion into a Y-H bond followed by a Si-C bond-forming sigma-bond metathes is of the resulting yttrium alkyl with silane.