Conversion of a Monodentate Amidinate鈥揋ermylene Ligand into Chelating Imine鈥揋ermanate Ligands (on Mononuclear Manganese Complexes)

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• 作者：Javier A. Cabeza ; Pablo Garc铆a-脕lvarez ; Enrique P茅rez-Carre帽o ; Diego Polo
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：August 18, 2014
• 年：2014
• 卷：53
• 期：16
• 页码：8735-8741
• 全文大小：327K
• ISSN：1520-510X

文摘

The unprecedented transformation of a terminal two-electron-donor amidinate鈥揼ermylene ligand into a chelating three-electron-donor 魏²-N,Ge-imine鈥揼ermanate ligand has been achieved by treating the manganese amidinate鈥揼ermylene complex [MnBr{Ge(ⁱPr₂bzam)^tBu}(CO)₄] (1; ⁱPr₂bzam = N,N鈥?bis(isopropyl)benzamidinate) with LiMe or Ag[BF₄]. In these reactions, which afford [Mn{魏²Ge,N-GeMe(ⁱPr₂bzam)^tBu}(CO)₄] (2) and [Mn{魏²Ge,N-GeF(ⁱPr₂bzam)^tBu}(CO)₄] (3), respectively, the anionic nucleophile, Me^{鈥?/sup> or F鈥?/sup>, ends on the Ge atom while an arm of the amidinate fragment migrates from the Ge atom to the Mn atom. In contrast, the reaction of 1 with AgOTf (OTf = triflate) leads to [Mn(OTf){Ge(iPr₂bzam)tBu}(CO)₄] (4), which maintains intact the amidinate鈥揼ermylene ligand. Complex 4 is very moisture-sensitive, leading to [Mn₂{渭鈥撐?sup>4Ge₂,O₂-Ge₂tBu₂(OH)₂O}(CO)₈] (5) and [iPr₂bzamH₂]OTf (6) in wet solvents. In 5, a novel digermanate(II) ligand, [tBu(OH)GeOGe(OH)tBu]2鈥?/sup>, doubly bridges two Mn(CO)₄ units. The structures of 1鈥?b>6 have been characterized by spectroscopic (IR, NMR) and single-crystal X-ray diffraction methods.}