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Document Type |
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Article In Journal |
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Document Title |
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Attachment of the new bulky ligand (Me3Si)(2)(Me2NMe2Si)C to Li, Hg, Al, Ga, and Sn. Crystal structures of [Li{C(SiMe3)(2)(SiMe2NMe2)}(THF)(2)], [Hg{C(SiMe3)(2)(SiMe2NMe2)}(2)], [Al{C(SiMe3)(2)(SiMe2NMe2)}X-2] (X = Cl, Ph), and [Ga{C(SiMe3)(2)(SiMe2NMe2)}Cl-2] Attachment of the new bulky ligand (Me3Si)(2)(Me2NMe2Si)C to Li, Hg, Al, Ga, and Sn. Crystal structures of [Li{C(SiMe3)(2)(SiMe2NMe2)}(THF)(2)], [Hg{C(SiMe3)(2)(SiMe2NMe2)}(2)], [Al{C(SiMe3)(2)(SiMe2NMe2)}X-2] (X = Cl, Ph), and [Ga{C(SiMe3)(2)(SiMe2NMe2)}Cl-2] |
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Document Language |
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Arabic |
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Abstract |
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The organolithium reagent [Li{C(SiMe3)(2)(SiMe2NMe2)(THF)(2)] (1) is readily obtained by reaction of the chloride (Me3Si)(2)(Me2NMe2Si)CCl with LiBu in THF (tetrahydrofuran) at low temperature. Reactions of 1 with HgBr2, AlCl3, GaCl3, and SnCl4 give [Hg{C(SiMe3)(2)(SiMe2NMe2)}(2)] (2), [Al(C(SiMe3)(2)(SiMe2NMe2)}Cl-2)] (3), Ga{C(SiMe3)(2)(SiMe2NMe2)}Cl-2 (5), and [Sn{C(SiMe3)(2)(SiMe2NMe2)}Cl-3] (6), respectively, and treatment of 3 with LiPh gives [Al(C(SiMe3)(2)(SiMe2NMe2)}Ph-2] (4). Crystal structure determinations have shown that there is intramolecular coordination of the N atom to the metal M, with formation of a planar four-membered C-Si-N-M ring, in 1, 3, 4, and 5 (but not 2). Engagement of the lone pair on N in coordination with Al in 3 results in an exceptionally long Si-N bond length of 1.875(2) Angstrom, some 0.16 Angstrom longer than that in 2 and in simple silylamines generally; the Si-N bond is possibly shorter in 4 (1.851(2) Angstrom) and 5 (1.858(4) Angstrom), and is markedly so in 1 (1.796(4) Angstrom), but still notably long. The lengths of the N-metal bonds in these compounds are similar to those between alkylamines and the metals in coordination compounds, indicating that at least in these systems the N atoms in the silylamines coordinate as strongly as those in the organic amines. Reaction of 6 with MeOH occurs exclusively at the Si-N bond to give [Sn{C(SiMe3)(2)(SiMe2OMe)}Cl-3], that of 2 with ICl or CF3CO2H gives [Hg{C(SiMe3)(2)(SiMe2Cl)}(2)] and [Hg{C(SiMe3)(2)(SiMe2O2CCF3)}(2)], respectively, and that of 1 with ICH2CH2I gives the iodide (Me3Si)(2)(Me2NMe2Si)CI. |
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Journal Name |
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ORGANOMETALLICS |
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Volume |
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18 |
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Issue Number |
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1 |
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Publishing Year |
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1999 AH
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Added Date |
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Saturday, June 14, 2008 |
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