2-(Aminomethyl)phenyl Complexes of Au(III), Mixed Au(III)/Ag(I), and Pd(II) with the 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand: Dancing of Palladacycles around a Juggler Ligand

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• 作者：Jos Vicente ; Mara-Teresa Chicote ; Elosa Martnez-Viviente ; Antonio-Jess Martnez-Martnez ; Nicols Snchez-Moya ; Peter G. Jones
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：September 6, 2010
• 年：2010
• 卷：49
• 期：17
• 页码：8099-8111
• 全文大小：1282K
• 年卷期：v.49,no.17(September 6, 2010)
• ISSN：1520-510X

文摘

The reaction of [Tl₂{μ-S,S-S₂C═C{C(O)Me}₂}] with [Au(C,N-C₆H₄CH₂NMe₂-2)Cl₂] (1:1) gives [{Au(C,N-C₆H₄CH₂NMe₂-2)}{S,S-S₂C═C{C(O)Me}₂}] (1) which, in turn, reacts with AgClO₄ (1:1) to give [{Au(C,N-C₆H₄CH₂NMe₂-2)}{Ag(OClO₃)}{S₂C═C{C(O)Me}₂}] (2). Complexes [{Au(C,N-C₆H₄CH₂NMe₂-2)}{Ag(X)(PPh₃)}{S₂C═C{C(O)Me}₂}] [X = OClO₃ (3), ONO₂ (4)] have been obtained by reaction of 1 with PPh₃ and AgClO₄ or AgNO₃, respectively (1:1:1). Complex 3 can also be obtained by reacting 2 with PPh₃ (1:1). Complexes [Pd(C,N-C₆H₄CH₂NR₂-2)(μ-Cl)]₂ (R = Me, H) react (i) with [Tl₂{S₂C═C{C(O)Me}₂}] and [PPN]Cl (0.5:1:1, PPN = Ph₃P═N═PPh₃) to form PPN[Pd(C,N-C₆H₄CH₂NR₂-2){S,S-S₂C═C{C(O)Me}₂}] [R = H (5a), Me (5b)], or (ii) with [Tl₂{S₂C═C{C(O)Me}₂}] (1:1) to form [{Pd(C,N-C₆H₄CH₂NR₂-2)}₂{μ-S,S,O-S₂C═C{C(O)Me}₂}] [R = H (6a), Me (6b)]. The trinuclear complexes [{Pd(C,N-C₆H₄CH₂NR₂-2)}₃{μ₃-O,S,S,O-S₂C═C{C(O)Me}₂}]ClO₄ [R = H (7a), Me (7b)] can be prepared by reacting the corresponding dinuclear complex 6a or 6b with [Pd(C,N-C₆H₄CH₂NR₂-2)(NCMe)₂]ClO₄ (1:1). The crystal structures of 1, 6b·CH₂Cl₂, and 7b·CH₂Cl₂ have been determined. NMR studies have been carried out to explain the solution behavior of these complexes. VT-NMR and line shape analysis for the species where R = Me (5b, 6b, 7b) have allowed the estimation of the activation parameters for these exchange processes.