Achim Kruckenberg, H. Wadepohl, L. Gade
Sep 10, 2013
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Influential Citations
30
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Journal
Organometallics
Abstract
The facile one-step synthesis of five new bis(diisopropylphosphinomethyl)amine ligands RN(CH2DIP)2 (DIP = diisopropylphosphine, R = Me–, iPr–, PhCH2–, 2-ThCH2–, and 2-FuCH2−) based on the use of the air-stable phosphonium salt [DIP(CH2OH)2]Cl is presented. The phosphonium salt cleanly reacts with primary amines to afford amine-bridged bisphosphine ligands with variable backbone substitution in good yields. These DIP ligands are useful model systems for their chiral bisphospholane analogues. The coordination chemistry of neutral nickel(II) complexes [(RDIP)NiCl2], [(RDIP)Ni(CH3)2], [(iPrDIP)Ni(Cl)CH2Si(CH3)3], and [(RDIP)Ni(CH2Ph)2], as well as coordinatively unsaturated cationic nickel(II) complexes [(RDIP)Ni(THF)CH3]+BArF– and [(RDIP)NiCH2Ph]+BArF–, has been studied by spectroscopic and X-ray diffraction methods. The cationic methyl complexes reacted cleanly with 2-butyne and 1,1-dimethylallene, yielding allylic complexes [(RDIP)Ni(pmcb)]+BArF– and [(RDIP)Ni(tma)]+BArF–, respectively (pmcb: η3-1,2,3,4,4-...