Activation of heteroallenes by coordinatively unsaturated nickel(II) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (Tp(Ph, Me)) ligand

作者：Abubekerov Mark; Eymann Leonard Y M; Gianetti Thomas L; Arnold John^*

来源：Dalton Transactions, 2016, 45(37): 14581-14590.

DOI：10.1039/c6dt01585a

Activation of sulfur containing heteroallenes by nickel(II) alkyl complexes supported by the bulky hydrotris(3-phenyl-5-methylpyrazolyl)borate (Tp(Ph,Me)) ligand is described. Exposure of Tp(Ph,Me) iCH(2)Ph (1a) and Tp(Ph,Me)NiCH(2)Si(CH3)(3) (1b) to CS2 resulted in formation of the insertion products Tp(Ph,Me)Ni(eta(2)-CS2)CH2Ph (2a) and Tp(Ph,Me)Ni(eta(2)-CS2)CH2Si(CH3)(3) (2b) in moderate yields. Reaction of 1a and MeNCS produced two species in a 1 : 1 ratio, identified as Tp(Ph,Me)Ni(eta(2)-MeNC)CH2Ph (3) and Tp(Ph,Me)Ni(eta(2)-MeNCS)SCH2Ph (4). Isolation of the unexpected insertion product (3) prompted an investigation into the activity of 1a-b in the presence of isocyanides (i.e. (BuNC)-Bu-t), which resulted in isolation of Tp(Ph,Me)Ni(eta(2)-(BuNC)-Bu-t) CH2Ph (5a) and Tp(Ph,Me)Ni(eta(2)-(BuNC)-Bu-t) CH2Si(CH3)(3) (5b). Similarly, reaction of 1a with OCS led to the isolation of a rare example of a Ni(I) carbonyl species Tp(Ph,Me)NiCO (6). Alternatively, complex 6 was also formed by exposure of 1a-b to an atmosphere of CO. Isolation of the intermediate species (Tp(Ph,Me)Ni(eta(2)-CO) CH2TMS (7b) and Tp(Ph,Me)Ni(CO)(C(O)R, (8a-b) with R = Ph, TMS)) shed light on the formation of such species.

• 出版日期2016