Group 13 and 14 Alkyl Derivatives of the Imido-Nitrido Metalloligand [{Ti(5-C5Me5)(<img src="http://p

详细信息    查看全文

• 作者：Mar&iacute ; a Garc&iacute ; a-Castro ; Avelino Mart&iacute ; n ; Miguel Mena ; Carlos Yé ; lamos
• 刊名：Organometallics
• 出版年：2007
• 出版时间：January 15, 2007
• 年：2007
• 卷：26
• 期：2
• 页码：408 - 416
• 全文大小：202K
• 年卷期：v.26,no.2(January 15, 2007)
• ISSN：1520-6041

文摘

The reactivity of the imido-nitrido trinuclear complex [{Ti(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)(images/entities/mgr.gif">-NH)}₃(images/entities/mgr.gif">₃-N)] (1) towardalkyl derivatives of group 13 and 14 elements has been investigated. Treatment of 1 with trialkyl derivativesof aluminum, gallium, or indium at room temperature afforded the adducts [R₃M{(images/entities/mgr.gif">₃-NH)₃Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">₃-N)}] (R = CH₂SiMe₃, M = Al (3), Ga (4), In (5); R = CH₂C₆H₅, M = Ga (6), In (7)). Theanalogous reaction of 1 with [AlMe₃] at 90 images/entities/deg.gif">C gave the methylaluminum derivative [MeAl{(images/entities/mgr.gif">₃-N)₂(images/entities/mgr.gif">₃-NH)Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">₃-N)}] (8) via methane elimination. Complexes 3 and 6 at this temperature gavealso monoalkyl complexes [RM{(images/entities/mgr.gif">₃-N)₂(images/entities/mgr.gif">₃-NH)Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">₃-N)}] (M = Al, R = CH₂SiMe₃ (9);M = Ga, R = CH₂C₆H₅ (11)), whereas the indium derivative 7 led to the indium(I) complex [In{(images/entities/mgr.gif">₃-N)(images/entities/mgr.gif">₃-NH)₂Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">₃-N)}] (12) and bibenzyl. Analogous chloromethylaluminum adducts [Me_nCl_3-nAl{(images/entities/mgr.gif">₃-NH)₃Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">₃-N)}] (n = 1 (13), 2 (14)) were obtained by treatment of 1 with[AlCl_3-nMe_n]. Reaction of the lithium reagent [Li(images/entities/mgr.gif">₄-N)(images/entities/mgr.gif">₃-NH)₂{Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">₃-N)}]₂ with tin,germanium, and silicon chloroalkyl derivatives [MClMe₃] gave the group 14 alkyl complexes [Me₃M{(images/entities/mgr.gif">₃-N)Ti₃(images/gifchars/eta.gif" BORDER=0 >⁵-C₅Me₅)₃(images/entities/mgr.gif">-NH)₂(images/entities/mgr.gif">₃-N)}] (M = Sn (15), Ge (16), Si (17)). The X-ray crystal structures of6, 7, 9, 13, 15, and 16 have been determined.