Synthesis and Unexpected Reactivity of Germyliumylidene Hydride [:GeH]+ Stabilized by a Bis(N-heterocyclic carbene)borate Ligand

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• 作者：Yun Xiong ; Tibor Szilv谩si ; Shenglai Yao ; Gengwen Tan ; Matthias Driess
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 13, 2014
• 年：2014
• 卷：136
• 期：32
• 页码：11300-11303
• 全文大小：285K
• ISSN：1520-5126

文摘

Employing the potassium salt of the monoanionic bis(NHC)borate 1 (NHC = N-Heterocyclic Carbene) enables the synthesis and isolation of the bis(NHC)borate-stabilized chlorogermyliumylidene precursor 2 in 61% yield. A Cl/H exchange reaction of 2 using potassium trisec.-butylborhydride as a hydride source leads to the isolation of the first germyliumylidene hydride [HGe:⁺] complex 3 in 91% yield. The Ge(II)鈥揌 bond in the latter compound has an unexpected reactivity as shown by the reaction with the potential hydride scavenger [Ph₃C]⁺[B(C₆F₅)₄]^{鈭?/sup>, furnishing the corresponding HGe: 鈫?CPh₃ cation in the ion pair 4 as initial product. Compound 4 liberates HCPh₃ in the presence of 3 to give the unusual dinuclear HGe: 鈫?Ge: cation in 5. The latter represents the first three-coordinate dicationic Ge(II) species stabilized by an anionic bis(NHC) chelate ligand and a Ge(II) donor. All novel compounds were fully characterized, including X-ray diffraction analyses.}