Facile Formation of Stable Tris(imido)phosphate Trianions as Their Tri- and Hexanuclear Pd(II) Complexes in Protic Solvents

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• 作者：Arvind K. Gupta ; S. Arun Dixith Reddy ; Ramamoorthy Boomishankar
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：July 1, 2013
• 年：2013
• 卷：52
• 期：13
• 页码：7608-7614
• 全文大小：346K
• 年卷期：v.52,no.13(July 1, 2013)
• ISSN：1520-510X

文摘

Employing Pd(OAc)₂, a facile deprotonation route to access the highly basic tris(alkylimido)phosphate trianions, [(RN)₃PO]^{3鈥?/sup> (R = tBu, cHex, or iPr), analogous to the orthophosphate (PO₄3鈥?/sup>) ion in polar and in protic solvents has been achieved. Trinuclear and prismatic Pd(II) clusters of these imido trianions having the formula {Pd₃[(NR)₃PO](OAc)₃}_n (n = 1 or 2) or as mixed-bridged clusters of the type {Pd₃[(NiPr)₃PO](OAc)₂(OR鈥?}₂ (R鈥?= Me or H) were isolated exclusively in all these reactions in which the trianionic species acts as a tripodal chelating ligand to the trinuclear Pd₃ unit. Reactivity studies aiming at the Pd(II) atoms in these clusters with nucleophilic reagents, such as primary amines (R鈥砃H₂), have led to a new trimeric cluster with the formula {Pd₃[(NR)₃PO](OAc)₃(R鈥砃H₂)₃} in which the tripodal coordination of the Pd鈥揘_imido moieties remained unaffected, exemplifying the robustness of the Pd₃ unit in all these clusters. We have also shown the catalytic activity of these Pd(II) complexes in Mizoroki鈥揌eck type coupling reactions in the presence of Cu(OAc)₂.}