Synthesis, Structure, and Reactivity of (tBu2PC2H4PtBu2)Ni(CH3)2 and {(tBu2PC2H4PtBu2)Ni}2(μ-H)2

摘要: Oxidative addition of CH3I to (dtbpe)Ni(C2H4) (dtbpe = tBu2PC2H4PtBu2) affords (dtbpe)Ni(I)CH3 (1). The reaction (dtbpe)NiCl2 or 1 with the stoichiometric quantity (tmeda)Mg(CH3)2 yields (dtbpe)Ni(CH3)2 (2). (dtbpe)Ni(I)CD3 (1-d3) and (dtbpe)Ni(CD3)2 (2-d6) have been prepared analogously. Thermolysis 2 in benzene {(dtbpe)Ni}2(μ-η2:η2-C6H6) (4). either 4 hydrogen (H2, HD, D2) gives {(dtbpe)Ni}2(μ-H)2 (3) isotopomers {(dtbpe)Ni}2(μ-H)(μ-D) (3-d) {(dtbpe)Ni}2(μ-D)2 (3-d2). According NMR spectra, structure 3 is dynamic solution. crystal structures determined by X-ray crystallography. Solution thermolysis reduction Mg* presence alkanes probably involves σ-complex-type intermediates [(dtbpe)Ni(η2-R‘H)] (R‘ e.g. C2H5, A). While nonisolated [(dtbpe)Ni0] σ-complexes A are exceedingly reactive intermediates, isolated represent easy handle starting complexes for [(d...