Unexpected Formal Aryl Insertion in a Cyclometalated Diphenylplatinum(IV) Complex: The First Seven-Membered Cyclometalated Platinum Compound Structurally Characterized

Cyclometalation of the (2-BrC 6 H 4 )CHNBzl imine via oxidative addition on [Pt II (Ph) 2 (SMe 2 ) 2 ] to produce the corresponding [Pt IV Br(Ph) 2 ( C C 5 H 3 CH N Bzl)(SMe 2 )] compound has been achieved, and the X-ray crystal structure of its triphenylphosphine derivative has been determined. The lability of the SMe 2 ligand in this complex enables the reductive elimination of a C 6 H 6 molecule and the formal insertion of the other phenyl ligand in the cyclometalated Pt−C bond, producing the first structurally characterized seven-membered cyclometalated platinum complex.