Well-Defined BisMETAMORPhos PdI-PdI Complex: Synthesis, Structural Characterization, and Reactivity

The formation of a bisMETAMORPhos PN-bridged dimeric Pd-I complex (3) from ligand 1 and Pd(dba)(2) is described. The addition of 1 to Pd(dba)2 initially leads to the formation of Pd-0 complex 2, which has a highly distorted tetrahedral environment and binds two neutral ligands 1. Complex 2 converts to {PdI}(2) complex 3 upon heating. Complex 3 consists of a completely flat PdPd core, with a PdPd bond length of 2.6199(4) angstrom, and the Pd centers display a highly distorted square planar coordination environment. The formation of complex 3 from 2 is suggested to proceed via an in situ comproportionation pathway. Initial decoordination of one ligand from 2 followed by oxidative addition of one neutral coordinated ligand arm leads to a 1-(PdH)-H-II complex. Insertion of free dba into the PdH bond generates a 1-PdIIdba complex that releases 1,5-diphenylpent-1-en-3-one via intra- or intermolecular protonolysis. Concomitantly, comproportionation with 1-Pd-0 yields 3. Complex 3 was found to function as a precatalyst in the SuzukiMiyaura cross-coupling of p-chloroacetophenone with good conversions.