Neutral and Ionic Aluminum, Gallium, and Indium Compounds Carrying Two or Three Terminal Ethynyl Groups
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- 作者：Marcus Schiefer ; N. Dastagiri Reddy ; Hans-Jü ; rgen Ahn ; Andreas Stasch ; Herbert W. Roesky ; A. Christine Schlicker ; Hans-Georg Schmidt ; Mathias Noltemeyer ; and Denis Vidovic
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：August 11, 2003
- 年：2003
- 卷：42
- 期：16
- 页码：4970 - 4976
- 全文大小：141K
- 年卷期：v.42,no.16(August 11, 2003)
- ISSN：1520-510X
文摘
The syntheses of the ionic compounds [Li+·2 dioxane (2,6-iPr2C6H3N(SiMe3)Al(C
CSiMe3)3)-]·0.75 dioxane (1),[(Li+)2·(dioxane)7]0.5 [2,6-iPr2C6H3N(SiMe3)Ga(CCSiMe3)3-]·1.5 dioxane (2), and [(Li+)2·(dioxane)7]0.5 [2,6-iPr2C6H3N(SiMe3)In(CCSiMe3)3-]·1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiCCSiMe3 are reported. The neutral ethynyl compounds Br-Al(CCtBu)2·2 THF (4), Cl-Ga(CCtBu)2·THF (5), Cl-In(CCtBu)2·2 THF (6), Al(CCtBu)3·C{N(Me)CMe}2 (7), Ga(CCtBu)3·dioxane (8), and In(CCtBu)3·NEt3 (9)have been obtained in good yields from the reaction of AlBr3, GaCl3, and InCl3 with LiCCtBu in the presence ofa Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and galliumcompounds with three terminal ethynyl groups Al(CCPh)3·NMe3 (10) and Ga(CCPh)3·NMe3 (11) have beenprepared by the reaction of AlH3·NMe3 or GaH3·NMe3 with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the threeterminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.
CSiMe3)3)-]·0.75 dioxane (1),[(Li+)2·(dioxane)7]0.5 [2,6-iPr2C6H3N(SiMe3)Ga(CCSiMe3)3-]·1.5 dioxane (2), and [(Li+)2·(dioxane)7]0.5 [2,6-iPr2C6H3N(SiMe3)In(CCSiMe3)3-]·1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiCCSiMe3 are reported. The neutral ethynyl compounds Br-Al(CCtBu)2·2 THF (4), Cl-Ga(CCtBu)2·THF (5), Cl-In(CCtBu)2·2 THF (6), Al(CCtBu)3·C{N(Me)CMe}2 (7), Ga(CCtBu)3·dioxane (8), and In(CCtBu)3·NEt3 (9)have been obtained in good yields from the reaction of AlBr3, GaCl3, and InCl3 with LiCCtBu in the presence ofa Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and galliumcompounds with three terminal ethynyl groups Al(CCPh)3·NMe3 (10) and Ga(CCPh)3·NMe3 (11) have beenprepared by the reaction of AlH3·NMe3 or GaH3·NMe3 with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the threeterminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.