Cooperative
Transition Metal/Lewis Acid Bond-Activation
Reactions by a Bidentate (Boryl)iminomethane Complex:
A Significant Metal–Borane Interaction Promoted by a Small
Bite-Angle LZ Chelate
posted on 2014-07-23, 00:00authored byBrandon
R. Barnett, Curtis E. Moore, Arnold L. Rheingold, Joshua S. Figueroa
The
synthesis of a three-coordinate Pt–borane complex featuring
a bidentate “LZ” (boryl)iminomethane (BIM)
ligand is reported. Unlike other LZ-type borane ligands featuring
a single-donor buttress, the small bite angle enforced by the BIM
ligand is shown to promote a significant metal–borane reverse-dative
σ-interaction akin to multiply strapped metalloboratranes. The
steric accessibility of the reactive Pt → B bond fostered by
the BIM ligand allows for a rich reactivity profile toward small molecules
that exploit metal–borane cooperative effects. The unligated
(boryl)iminomethane BIM is also synthetically accessible
and functions as a Frustrated Lewis Pair (FLP). The ability of the
free BIM to effect bond activation reactions is contrasted with the
behavior seen in the corresponding platinum-bound complexes.