Seifert Annekathrin, Linti Gerald
Anorganisch-Chemisches Institut, Universitat Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.
Inorg Chem. 2008 Dec 1;47(23):11398-404. doi: 10.1021/ic801437n.
By reaction of the gallium(I) derivative Ga(4)tmp(4) (tmp = 2,2,6,6-tetramethylpiperidino) with Cr(CO)(5)(cyclo-octene), Co(2)(CO)(8), and Ni(cyclooctadiene)(2), respectively, the Gatmp complexes [Cr(CO)(5)Gatmp], (CO)(3)Cr(mu(2)-Gatmp)(3)Cr(CO)(3), (CO)(3)Co(mu(2)-Gatmp)(2)Co(CO)(3), and (tmpGa)(2)Ni(mu(2)-Gatmp)(3)Ni(Gatmp)(2) were obtained. The latter are described as derivatives of the binuclear metal carbonyls Cr(2)(CO)(9), Co(2)(CO)(8), and Ni(2)(CO)(7), where some or all carbonyls are replaced by the amino gallylene group. All compounds are characterized by spectroscopy and crystal structure analysis. The change of the bonding situation from localized two-center gallium metal bonds in the chromium derivative to three-center bonds in the cobalt complex is discussed by means of density functional theory calculations.
通过镓（I）衍生物Ga(4)tmp(4)（tmp = 2,2,6,6 - 四甲基哌啶基）分别与Cr(CO)(5)(环辛烯)、Co(2)(CO)(8)和Ni(环辛二烯)(2)反应，得到了Gatmp配合物[Cr(CO)(5)Gatmp]、(CO)(3)Cr(μ(2)-Gatmp)(3)Cr(CO)(3)、(CO)(3)Co(μ(2)-Gatmp)(2)Co(CO)(3)和(tmpGa)(2)Ni(μ(2)-Gatmp)(3)Ni(Gatmp)(2)。后者被描述为双核金属羰基化合物Cr(2)(CO)(9)、Co(2)(CO)(8)和Ni(2)(CO)(7)的衍生物，其中部分或全部羰基被氨基镓烯基团取代。所有化合物均通过光谱学和晶体结构分析进行表征。借助密度泛函理论计算，讨论了从铬衍生物中局域化的双中心镓 - 金属键到钴配合物中三中心键的键合情况变化。
