title: Formation and Reactivity of a C-P-N-Sc Four-Membered Ring: H2, O2, CO, Phenylsilane, and Pinacolborane Activation.
abstract: Reaction of scandium dimethyl complex LScMe2(L=[2-{N(DIPP)C(Ph)N}C6H4CH=N(DIPP)]-, DIPP=2,6-(iPr)2C6H3) (2) with bulky phosphine ArPH2(Ar=2,6-{3,5-(Me)2C6H3}2C6H3) gives an unprecedented scandium 2,3-azaphosphametallacyclobutane complex L'Sc (L'=[2-{N(DIPP)C(Ph)N}C6H4C(H)P(2,6-{3,5-(CH3)2C6H3}2C6H3)N(DIPP)]3-) (3) that contains a C-P-N-Sc four-membered ring. Complex 3 was characterized by X-ray crystallography, revealing a short distance between the Sc and P atoms (2.786(1) Å), but without a direct Sc-P bonding interaction. The formation of 3 involves a complete cleavage of the imino bond of the tridentate ligand L and C-P and N-P bond coupling. Complex 3 not only activates H2under mild conditions to give a H-H bond cleavage product, but also reacts with O2, CO, phenylsilane, and pinacolborane to produce novel products through cleavage and formation of various bonds.
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
authors.forename: Jiliang
authors.initials: J
authors.lastname: Zhou
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
authors.forename: Li
authors.initials: L
authors.lastname: Xiang
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
authors.forename: Jingjing
authors.initials: J
authors.lastname: Guo
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
authors.forename: Xuebing
authors.initials: X
authors.lastname: Leng
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
authors.forename: Yaofeng
authors.initials: Y
authors.lastname: Chen
keywords: Lewis acids; Lewis bases; insertion; phosphorus; scandium