First-Row Transition-Metal Chloride Complexes of the Wide Bite-Angle Diphosphine iPrDPDBFphos and Reactivity Studies of Monovalent Nickel

详细信息    查看全文

• 作者：Elodie E. Marlier ; Stephen J. Tereniak ; Keying Ding ; Jenna E. Mulliken ; Connie C. Lu
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：October 3, 2011
• 年：2011
• 卷：50
• 期：19
• 页码：9290-9299
• 全文大小：1100K
• 年卷期：v.50,no.19(October 3, 2011)
• ISSN：1520-510X

文摘

The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as ^iPrDPDBFphos) has been metalated with transition metal dichlorides of zinc, cobalt, and nickel to yield (^iPrDPDBFphos)MCl₂ complexes. Within these compounds, the diphosphine ^iPrDPDBFphos adapts a wide range of bite angles (115 to 180掳) as determined by X-ray crystallography. A three-coordinate planar Ni(I) species was isolated from the reduction of (^iPrDPDBFphos)NiCl₂ with KC₈. Low-temperature electron paramagnetic resonance (EPR) measurements of (^iPrDPDBFphos)NiCl allow the determination of g values (2.09, 2.14, 2.37) and hyperfine coupling constants to two ³¹P nuclei, A_iso = 46 脳 10^鈥? cm^鈥?, and one ³⁷Cl/³⁵Cl nucleus, A = (12, 0.7, 35) 脳 10^鈥? cm^鈥?. Density functional theory (DFT) studies reveal the nature of the magnetic orbital to be d_xy, which has 蟽-antibonding and 蟺-antibonding interactions with the phosphorus and chloride atoms, respectively. The monovalent nickel complex reacts with substrates containing C鈥揦 bonds; and in the case of vinyl chloride, a Ni(II) vinyl species (^iPrDPDBFphos)Ni(CH鈺怌H₂)Cl is generated along with the Ni(II) dichloride complex. The monovalent Ni(I) chloride is an active catalyst in the Kumada cross-coupling reaction of vinyl chloride and phenyl Grignard reagent.