Exceptional Behavior of Ni2O2 Species Revealed by ESI-MS and MS/MS Studies in Solution. Application of Superatomic Core To Facilitate New Chemical Transformations

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• 作者：Dmitry B. Eremin ; Valentine P. Ananikov
• 刊名：Organometallics
• 出版年：2014
• 出版时间：November 24, 2014
• 年：2014
• 卷：33
• 期：22
• 页码：6352-6357
• 全文大小：395K
• ISSN：1520-6041

文摘

Acetonitrile solutions of nickel(II) acetylacetonate, which is ubiquitously used in different fields of organometallic chemistry and catalysis, were investigated by means of electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS). The detected Ni₂(acac)₃p>+p> ion with the binuclear Ni₂O₂ core underwent a wide range of reactions after collision-induced dissociation, leading to a variety of products. Activation of C鈥揌, C鈥揅, and C鈥揙 bonds was observed involving the binuclear nickel complex. In sharp contrast, similar ions involving mononuclear and trinuclear nickel species did not show such exceptional behavior. The findings may open a fascinating direction in the field of superatoms to develop new chemical transformations for organometallic chemistry and catalysis. The higher relative stability of binuclear species was also observed in ESI mass spectra of copper and vanadyl complexes with acetylacetonate ligands, Cu₂(acac)₃p>+p> and (VO)₂(acac)₃p>+p>. An important point concerns the purity of the studied solutions, since even a trace level of contaminants has drastically diminished the outcome of the mechanistic studies.