Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
Dalton Trans. 2018 Nov 13;47(44):15835-15844. doi: 10.1039/c8dt03166e.
The reaction of [CH{(CMe)(2,6-iPr2C6H3N)}2]GeCl with LiN(SiMe3)2 was previously reported, which led to the formation of a hetero-fulvene type germylene, [CH{(CMe)(C[double bond, length as m-dash]CH2)(2,6-iPr2C6H3N)}2]Ge through the deprotonation of the C-H bond from the methyl substituents. In this paper, we attempted the analogous reaction with (Dipp)NCMeCHCOMeGeCl using LiN(SiMe3)2 which gave rise to a metathesis product, (Dipp)NCMeCHCOMeGeN(SiMe3)2 (2). However, the reactions of 2 with [M2Cl2(μ-Cl)2(η5-Cp*)2] (M = Rh and Ir) resulted in cyclometallated Rh and Ir complexes through the activation of the C-H bond from the germylene ligand. The complexes were characterized by single crystal X-ray analysis, which authenticated the presence of Ge-Rh and Ge-Ir bonds. DFT studies have been performed to understand the mechanism.
此前曾报道过 [CH{(CMe)(2,6-iPr2C6H3N)}2]GeCl 与 LiN(SiMe3)2 的反应，该反应导致通过甲基取代基的 C-H 键去质子化，形成了杂富烯型锗亚基 [CH{(CMe)(C[double bond, length as m-dash]CH2)(2,6-iPr2C6H3N)}2]Ge。在本文中，我们尝试使用 LiN(SiMe3)2 对 (Dipp)NCMeCHCOMeGeCl 进行类似的反应，得到了复分解产物 (Dipp)NCMeCHCOMeGeN(SiMe3)2（2）。然而，2 与 [M2Cl2(μ-Cl)2(η5-Cp*)2]（M = Rh 和 Ir）的反应通过锗亚基中 C-H 键的活化导致了 Rh 和 Ir 配合物的形成。通过单晶 X 射线分析对配合物进行了表征，证实了 Ge-Rh 和 Ge-Ir 键的存在。进行了 DFT 研究以了解反应机理。
