Group 2 and 12 Metal Gallyl Complexes Containing Unsupported Ga-M Covalent Bonds (M = Mg, Ca, Sr, Ba, Zn, Cd)
Group 2 and 12 Metal Gallyl Complexes Containing Unsupported Ga-M Covalent Bonds (M = Mg, Ca, Sr, Ba, Zn, Cd)
复制标题
DOI：
10.1021/om1001606
复制
发表时间：
2010-11-08
期刊：
影响因子：
2.8
通讯作者：
Woodul, William D.
中科院分区：
文献类型：
--
作者：
Bonello, Owen;Jones, Cameron;Woodul, William D.
报道了阴离子镓(I)杂环[:Ga(DAB)](-) (DAB = {N(Dip)C(H)}(2) Dip = C6H3-Pr-2(i),-2,6）与几种第2族和第12族金属卤化物络合物的反应。用 2 当量的 [K(tmeda)][:Ga(DAB)] 处理原位生成的 [MI2(tmeda)(n)]（M = Ca、Sr、Ba；tmeda = N,N,N',N'-四甲基乙二胺）导致盐消除并形成中性金属没食子络合物反式-[M{Ga(DAB)}(2)(tmeda)(2)]。 [(Nacnac)MgI(OEt2)] (Nanac = {N(Dip)C(Me)}(2)CH) 与 [K(tmeda)][:Ga(DAB)] 反应得到 [(Nacnac)(kappa(1)-tmeda)Mg{Ga(DAB)}]。我们对所有配合物进行了重新晶体学表征，并在溶液中显示出异构现象，后一种化合物的异构现象已通过变温核磁共振波谱进行了研究。 [K(tmeda)][:Ga(DAB)] 与 [MX2(tmeda)]（M = Zn，X = Br；M = Cd，X = 1）的 1:1 反应生成 [(tmeda)MX{Ga(DAB)}]，其中镉的例子是第一个带有 Ga-Cd 键的分子配合物。尝试将这些化合物还原为低价物质，例如[{(DAB)Ga}MM{Ga(DAB)}]，未成功。用 [K(tmeda)][:Ga(DAB)] 处理 [(Nacnac)Zn(mu-Br)(2)Li(OEt2)(2)] 得到 [(Nacnac)Zn{Ga(DAB)}]，报告了其 X 射线晶体结构。
Reactions of the anionic gallium(I) heterocycle [:Ga(DAB)](-) (DAB = {N(Dip)C(H)}(2) Dip = C6H3-Pr-2(i),-2,6) with several group 2 and 12 metal halide complexes are reported. Treatment of in situ generated [MI2(tmeda)(n)] (M = Ca, Sr, Ba; tmeda = N,N,N',N'-tetramethylethylenediamine) with 2 equiv of [K(tmeda)][:Ga(DAB)] leads to salt elimination and formation of the neutral metal gallyl complexes trans-[M{Ga(DAB)}(2)(tmeda)(2)]. Reaction of [(Nacnac)MgI(OEt2)] (Nanac = {N(Dip)C(Me)}(2)CH) with [K(tmeda)][:Ga(DAB)] gives [(Nacnac)(kappa(1)-tmeda)Mg{Ga(DAB)}]. All complexes we re crystallographically characterized and display isomerism in solution, which for the latter compound has been investigated by variable-temperature NMR spectroscopy. The 1:1 reactions of [K(tmeda)][:Ga(DAB)] with [MX2(tmeda)] (M = Zn, X = Br; M = Cd, X = 1) yield [(tmeda)MX{Ga(DAB)}], the cadmium example of which is the first molecular complex bearing a Ga-Cd bond. Attempts to reduce these compounds to low-valent species, e.g. [{(DAB)Ga}MM{Ga(DAB)}], were unsuccessful. Treating [(Nacnac)Zn(mu-Br)(2)Li(OEt2)(2)] with [K(tmeda)][:Ga(DAB)] gave [(Nacnac)Zn{Ga(DAB)}], the X-ray crystal structure of which is reported.