Anorganische Chemie II, Organometallics and Materials Chemistry, Ruhr-Universität Bochum, Bochum, Germany.
Dalton Trans. 2011 Dec 14;40(46):12570-7. doi: 10.1039/c1dt11386k. Epub 2011 Oct 11.
The reactions of heteroleptic GaCp*/CO containing transition metal complexes of iron and cobalt, namely [(CO)(3)M(μ(2)-GaCp*)(m)M(CO)(3)] (Cp* = pentamethylcyclopentadienyl; M = Fe, m = 3; M = Co, m = 2) and [Fe(CO)(4)(GaCp*)], with ZnMe(2) in toluene and the presence of a coordinating co-solvent were investigated. The reaction of the iron complex [Fe(CO)(4)(GaCp*)] with ZnMe(2) in presence of tetrahydrofurane (thf) leads to the dimeric compound [(CO)(4)Fe{μ(2)-Zn(thf)(2)}(2)Fe(CO)(4)] (1). Reaction of [(CO)(3)Fe(μ(2)-GaCp*(3))Fe(CO)(3)] with ZnMe(2) and stoichiometric amounts of thf leads to the formation of [(CO)(3)Fe{μ(2)-Zn(thf)(2)}(2)(μ(2)-ZnMe)(2)Fe(CO)(3)] (2) containing {Zn(thf)(2)} as well as ZnMe ligands. Using pyridine (py) instead of thf leads to [(CO)(3)Fe{μ(2)-Zn(py)(2)}(3)Fe(CO)(3)] (3) via replacement of all GaCp* ligands by three{Zn(py)(2)} groups. In contrast, reaction of [(CO)(3)Co(μ(2)-GaCp*)(2)Co(CO)(3)] with ZnMe(2) in the presence of py or thf leads in both cases to the formation of [(CO)(3)Co{μ(2)-ZnL(2)}(μ(2)-ZnCp*)(2)Co(CO)(3)] (L = py (4), thf (5)) via replacement of GaCp* with {Zn(L)(2)} units as well as Cp* transfer from the gallium to the zinc centre. All compounds were characterised by NMR spectroscopy, IR spectroscopy, single crystal X-ray diffraction and elemental analysis.
研究了含有铁和钴的异双核 GaCp*/CO 配合物的反应，即 [(CO)(3)M(μ(2)-GaCp*)(m)M(CO)(3)]（Cp*= 五甲基环戊二烯基；M=Fe，m=3；M=Co，m=2）和 [Fe(CO)(4)(GaCp*)]，与 ZnMe(2) 在甲苯中，并存在配位共溶剂。在四氢呋喃 (thf) 的存在下，铁配合物 [Fe(CO)(4)(GaCp*)] 与 ZnMe(2) 的反应导致二聚化合物 [(CO)(4)Fe{μ(2)-Zn(thf)(2)}(2)Fe(CO)(4)]（1）的形成。[(CO)(3)Fe(μ(2)-GaCp*(3))Fe(CO)(3)] 与 ZnMe(2) 和化学计量的 thf 反应导致形成 [(CO)(3)Fe{μ(2)-Zn(thf)(2)}(2)(μ(2)-ZnMe)(2)Fe(CO)(3)]（2），其中包含{Zn(thf)(2)}和 ZnMe 配体。使用吡啶 (py) 代替 thf 导致通过三个{Zn(py)(2)}基团取代所有 GaCp配体，生成 [(CO)(3)Fe{μ(2)-Zn(py)(2)}(3)Fe(CO)(3)]（3）。相比之下，[(CO)(3)Co(μ(2)-GaCp)(2)Co(CO)(3)] 与 ZnMe(2) 在 py 或 thf 的存在下反应，在两种情况下都会形成[(CO)(3)Co{μ(2)-ZnL(2)}(μ(2)-ZnCp*)(2)Co(CO)(3)]（L=py（4），thf（5）），通过 GaCp* 被{Zn(L)(2)}单元以及 Cp* 从镓到锌中心的转移取代。所有化合物均通过 NMR 光谱、IR 光谱、单晶 X 射线衍射和元素分析进行了表征。
