Comparative Study of Mono- and Dinuclear Complexes of Late 3d-Metal Chlorides with N,N-Dimethylformamide in the Gas phase

详细信息    查看全文

• 作者：Lucie Ducha虂č ; kova虂 ; Jana Roithova虂 ; Petr Milko ; Jan Z虒abka ; Nikos Tsierkezos ; Detlef Schro虉der
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：February 7, 2011
• 年：2011
• 卷：50
• 期：3
• 页码：771-782
• 全文大小：1153K
• 年卷期：v.50,no.3(February 7, 2011)
• ISSN：1520-510X

文摘

Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)_nMCl]⁺ and [(DMF)_nM₂Cl₃]⁺, of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory. The mononuclear complexes [(DMF)_nMCl]⁺ almost exclusively lose neutral DMF upon collisional activation with the notable exception of the copper complex, for which also a reduction from Cu^II to Cu^I concomitant with the release of atomic chlorine is observed. For the dinuclear clusters, there exists a competition between loss of a DMF ligand and cluster degradation via loss of neutral MCl₂ with decreasing cluster stability from cobalt to zinc. For the specific case of [(DMF)_nZnCl]⁺ and [(DMF)_nZn₂Cl₃]⁺, ion-mobility mass spectrometry indicates the existence of two isomeric cluster ions in the case of [(DMF)₂Zn₂Cl₃]⁺ which corroborates parallel theoretical predictions.