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• W2022110660 abstract "The insertion reactions of CNMe and CN-t-Bu with , 1, have been investigated to evaluate the stereoelectronic influence of the Cp∗ ligand on the competitive 1,2-silyl shift and reduction coupling pathways previously observed for . Under ambient conditions the addition of CNMe to 1 proceeds with the sequential formation of , 2, and , 3. Alternatively, the addition of excess CNMe below -5δC to 1 occurs with reductive coupling to produce , 4, In contrast, the addition of two equivalents of CN-t-Bu to 1 does not afford the corresponding cyclic enamide species but proceeds with the sequential formation of , 5, and , 6. The molecular structures of 3 and 6 have been determined by X-ray crystallography. The puckered 1-sila-3,5-diaza-4-hafnacyclohexane ring of 3 adopts a chair conformation with the folding along the N…N' vector being 19.3° out of the N', Hf, N plane toward the smaller Cp ligand and the folding along the C(1)…C(1)' vector being 43.3° in the opposite direction toward the Cp∗ ligand. The molecular structure of 6 is consistent with nucleophilic attack of CN-t-Bu at the η2-immunoacyl carbon of 5 occurring exclusively from the side opposite to the Cp∗ ligand. The second equivalentof CN-t-Bu displaces the η2-iminoacyl group away from the Hf atom, eventually placing the resultant imine group of 6 syn to the Cp∗ ligand." @default.
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• W2022110660 date "1995-01-01" @default.
• W2022110660 modified "2023-09-25" @default.
• W2022110660 title "Stereochemical influence of the pentamethylcyclopentadienyl ligand on the isocyanide insertion reactions of the 1-sila-3-hafnacyclobutane complex," @default.
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• W2022110660 doi "https://doi.org/10.1016/0277-5387(94)00322-6" @default.
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