New organogermanium cations [RGe(OCH2CH2NME2)(2)](+) with intramolecular N -> Ge coordination bonds

作者：Portnyagin I A; Lunin V V; Nechaev M S^*

来源：Russian Chemical Bulletin, 2007, 56(5): 926-934.

DOI：10.1007/s11172-007-0141-x

• organogermanium compounds
• hypercoordinated compounds
• germyl cations
• intramolecular coordination bonds
• H-1 and C-13 NMR spectroscopy
• density functional method

New organohalogermanes RGe(OCH2CH2NMe2)(2)X (R = Ph, X = I (5); R = Me, X = Cl (6) or I (7)) with an intramolecular N -> Ge coordination bond were synthesized. According to the H-1 and C-13 NMR spectroscopic data, iodides 5 and 7 exist in solution as ionic compounds with the pentacoordinated germanium atom. In solution of compound 4 (R = Ph, X = Cl), there is an equilibrium between the ionic and covalent forms. The equilibrium shifts toward the ionic form with increasing solvent polarity or temperature. In solution, chloride 6 is a covalent compound. The structures and relative stabilities of different isomers of compounds 4-7 were studied by quantum chemical calculations at the density functional level of theory.

• 出版日期2007-5