Synthesis and Structures of Mono- and Bis(amidinate) Complexes of Aluminum
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- 作者：Martyn P. Coles ; Dale C. Swenson ; Richard F. Jordan ; and Victor G. Young ; Jr.
- 刊名：Organometallics
- 出版年：1997
- 出版时间：November 25, 1997
- 年：1997
- 卷：16
- 期：24
- 页码：5183 - 5194
- 全文大小：478K
- 年卷期：v.16,no.24(November 25, 1997)
- ISSN：1520-6041
文摘
The synthesis and structures of mono- andbis(amidinate) aluminum complexes aredescribed. The reaction of AlMe3 and 1 equiv ofcarbodiimide, R'N=C=NR', affords{MeC(NR')2}AlMe2 (1a, R'= iPr; 1b, R' = Cy =cyclohexyl). The reaction of R'N=C=NR'with MeLi or tBuLi generatesLi[RC(NR')2] (2a, R = Me, R' =iPr; 3a, R =tBu, R' =iPr; 3b,R = tBu, R' = Cy; 3c, R =tBu, R' = SiMe3).2a, 3a, and 3b may be isolated orreacted insitu, while attempted isolation of 3c gave[Li(tBuCN){
ges/entities/mgr.gif">-N(SiMe3)2}]2(3d). The reaction of1 equiv of AlCl3 with 2a or3a-c affords{RC(NR')2}AlCl2 (4a, R= Me; 5a-c, R =tBu), andthe reaction of AlMe2Cl with3a-c affords{tBuC(NR')2}AlMe2(6a-c). Alkylation of5a,bwith 2 equiv of PhCH2MgCl orMe3CCH2Li yields{tBuC(NR')2}Al(CH2Ph)2(7a,b) or{tBuC(NR')2}Al(CH2CMe3)2(8a,b). The reaction of 0.5 equiv ofAlCl3 with 2a or 3a,byields{RC(NR')2}2AlCl (9a, R =Me; 10a,b, R =tBu). Complexes 1b,3d, 4a, 5a,b,6b, 8b, 9a, and10a,b have been characterized by X-raycrystallography. The crystallographic resultsestablish that steric interactions between the R and R' groupsinfluence the R'-N-Al angleand, hence, the steric environment at aluminum.