Preparation of Benzyne Complexes of Group 10 Metals by Intramolecular Suzuki Coupling ofortho-Metalated Phenylboronic Esters: Molecular Structure of the First Benzyne-Palladium(0) Complex

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Abstract
A series of nickel(II) and palladium(II) aryl complexes substituted in the ortho position of the aromatic ring by a (pinacolato)boronic ester group, [MBr{o-C6H4B(pin)}L2] (M = Ni, L2 = 2PPh3 (2a), 2PCy3 (2b), 2PEt3 (2c), dcpe (2d), dppe (2e), and dppb (2f); M = Pd, L2 = 2PPh3 (3a), 2PCy3 (3b), and dcpe (3d)), has been prepared. Many of these complexes react readily with KOtBu to form the corresponding benzyne complexes [M(η2-C6H4)L2] (M = Ni, L2 = 2PPh3 (4a), 2PCy3 (4b), 2PEt3 (4c), dcpe (4d); M = Pd, L2 = 2PCy3 (5b)). This reaction can be regarded as an intramolecular version of a Suzuki cross-coupling reaction, the driving force for which may be the steric interaction between the boronic ester group and the phosphine ligands present in the precursors 2 and 3. Complex 3d also reacts with KOtBu, but in this case disproportionation of the initially formed η2-C6H4 complex (5d) leads to a 1:1 mixture of a novel dinuclear palladium(I) complex, [(dcpe)Pd(μ2-C6H4)Pd(dcpe)] (6), and a 2,2‘-biphenyldiyl complex, [Pd(2,2‘-C6H4C6H4)(dcpe)] (7d). Complexes 2a, 3b, 3d, 4b, 5b, 6, and 7d have been structurally characterized by X-ray diffraction; complex 5b is the first example of an isolated benzyne-palladium(0) species.

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