- Preparation of Aryne-Nickel Complexes from ortho-Borylaryl Triflates
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A facile method for preparing diverse aryne-nickel complexes from readily synthesized ortho-borylaryl triflates is described. Exploratory synthetic applications, including the synthesis of 1,2-difunctionalized arenes, based on the nucleophilic character of the aryne-nickel complexes are also demonstrated.
- Sumida, Yuto,Sumida, Tomoe,Hashizume, Daisuke,Hosoya, Takamitsu
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supporting information
p. 5600 - 5603
(2016/11/17)
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- Preparation of benzyne complexes of group 10 metals by intramolecular Suzuki coupling of ortho-metalated phenylboronic esters: Molecular structure of the first benzyne-palladium(0) complex
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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.
- Retboll, Mikael,Edwards, Alison J.,Rae, A. David,Willis, Anthony C.,Bennett, Martin A.,Wenger, Eric
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p. 8348 - 8360
(2007/10/03)
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