Stender M, Eichler B E, Hardman N J, Power P P, Prust J, Noltemeyer M, Roesky H W
Institut für Anorganische Chemie der Universität Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany.
Inorg Chem. 2001 Jun 4;40(12):2794-9. doi: 10.1021/ic001311d.
A series of group 13 metal complexes featuring the beta-diketiminate ligand (C(6)H(3)-2,6-i-Pr(2))NC(Me)CH (i.e., Dipp(2)nacnac, Dipp = C(6)H(3)-2,6-i-Pr(2)) have been prepared and spectroscopically and structurally characterized. The chloride derivatives Dipp(2)nacnacMCl(2) (M = Al (3), Ga (5), In (8)) were isolated in good yield by the reaction of 1 equiv of Dipp(2)nacnacLi.Et(2)O (2) and the respective metal halides. The iodide derivatives Dipp(2)nacnacMI(2) (M = Al (4), Ga (6), In (9)), which are useful for reduction to afford M(I) species, were made by a variety of routes. Thus, 4 was obtained by treatment of the previously reported Dipp(2)nacnacAlMe(2) with I(2), whereas the gallium analogue 6 was obtained as a product of the reaction of "GaI" with Dipp(2)nacnacLi.Et(2)O, and 9 was obtained by direct reaction of InI(3) and the lithium salt. The methyl derivatives Dipp(2)nacnacMMe(2) (M = Ga (7), In (10)), which are analogous to the previously reported Dipp(2)nacnacAlMe(2), were synthesized by the reaction of GaMe(3) with Dipp(2)nacnacH (1) or by reaction of the indium chloride derivative 8 with 2 equiv of MeMgBr in diethyl ether. The compounds 3-10 exist as colorless, air- and moisture-sensitive crystalline solids. Their X-ray crystal structures feature nearly planar C(3)N(2) arrays in the Dipp(2)nacnac ligand backbone with short C-C and C-N distances that are consistent with a delocalized structure. However, there are large dihedral angles between the C(3)N(2) plane and the N(2)M metal coordination plane which have been attributed mainly to steric effects. The relatively short M-N distances are consistent with the coordination numbers of the metals and the normal/dative character of the nitrogen ligands. The compounds were also characterized by (1)H and (13)C NMR spectroscopy. (1)H NMR data for 7 revealed equivalent methyl groups whereas the spectrum of 10 displayed two In-Me signals which indicated that ring wagging was slow on the (1)H NMR time scale.
已制备出一系列以β-二酮亚胺配体(C(6)H(3)-2,6-i-Pr(2))NC(Me)CH（即Dipp(2)nacnac，Dipp = C(6)H(3)-2,6-i-Pr(2)）为特征的第13族金属配合物，并通过光谱和结构表征进行了研究。通过使1当量的Dipp(2)nacnacLi·Et(2)O（2）与相应的金属卤化物反应，以良好的产率分离出氯化物衍生物Dipp(2)nacnacMCl(2)（M = Al (3)、Ga (5)、In (8)）。碘化物衍生物Dipp(2)nacnacMI(2)（M = Al (4)、Ga (6)、In (9)）可通过多种途径制得，这些衍生物可用于还原以得到M(I)物种。因此，4是通过用I(2)处理先前报道的Dipp(2)nacnacAlMe(2)得到的，而镓类似物6是作为“GaI”与Dipp(2)nacnacLi·Et(2)O反应的产物得到的，9是通过InI(3)与锂盐直接反应得到的。甲基衍生物Dipp(2)nacnacMMe(2)（M = Ga (7)、In (10)）与先前报道的Dipp(2)nacnacAlMe(2)类似，通过GaMe(3)与Dipp(2)nacnacH (1)反应或通过氯化铟衍生物8与2当量的MeMgBr在乙醚中反应合成。化合物3 - 10以无色、对空气和湿气敏感的结晶固体形式存在。它们的X射线晶体结构在Dipp(2)nacnac配体主链中具有近乎平面的C(3)N(2)阵列，C - C和C - N距离较短，这与离域结构一致。然而，C(3)N(2)平面与N(2)M金属配位平面之间存在较大的二面角，这主要归因于空间效应。相对较短的M - N距离与金属的配位数以及氮配体的正常/给予性质一致。这些化合物还通过(1)H和(13)C NMR光谱进行了表征。7的(1)H NMR数据显示甲基等效，而10的光谱显示两个In - Me信号，这表明在(1)H NMR时间尺度上环摆动缓慢。
