Synthesis of -Imino Carbonyl Enolato Complexes by Reaction of Nickel(II), Palladium(II), and Copper(II) Acetates with
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- 作者：Marino Basato ; Umberto Vettori ; Augusto C. Veronese ; Alfonso Grassi ; and Giovanni Valle
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：December 28, 1998
- 年：1998
- 卷：37
- 期：26
- 页码：6737 - 6745
- 全文大小：209K
- 年卷期：v.37,no.26(December 28, 1998)
- ISSN：1520-510X
文摘
Nickel(II), palladium(II), and copper(II) acetates undertake exchange reaction with the 
-enaminodiones (MeOCO)(RCO)CC(R')NH2 (R = Me, OMe; R' = Et, EtOCO) in ethanol to give the neutral complexes [M((MeOCO)(RCO)CC(R')NH)2] (1-8) [R = Me, R' = Et: M = Ni (1), Pd (2a,b), Cu (3); R = Me, R' = EtOCO: M = Ni(4), Pd (5), Cu (6); R = MeO, R' = Et, M = Pd (7a,b); R = MeO, R' = EtOCO, M = Pd (8a,b)]. The trifunctionalN,O,O ligands act in all cases as bidentate through the imino and one carbonyl group. Complexes 1-8 are allmonomers with a square planar geometry. Nickel and palladium complexes show more than one form in the solidstate. For example the palladium complex 2 has been synthesized in two forms a and b, which differ in theconformation of the methoxy carbonyl substituent of the chelate ring, while the third isomer or conformer isobtained by thermal treatment at 120 
C. Complexes 7 and 8 also exhibit two forms which differ in the degreeof intermolecular hydrogen bonding. Both 7b and 8b crystallize in monoclinic unit cells [7b: space group P21/n,a = 11.963(2), b = 8.438(1), c = 19.637(2) Å, = 94.2(1). 8b: P21/c, a = 10.698(2), b = 14.902(2), c =13.918(2) Å, = 95.2(1)] containing four molecules linked by intermolecular hydrogen bonding [N-H···O=C,2.14-2.36 Å]. All complexes are thermally stable and volatile. Their mass spectra exhibit intense molecular ionpeaks under EI mass conditions.
-enaminodiones (MeOCO)(RCO)CC(R')NH2 (R = Me, OMe; R' = Et, EtOCO) in ethanol to give the neutral complexes [M((MeOCO)(RCO)CC(R')NH)2] (1-8) [R = Me, R' = Et: M = Ni (1), Pd (2a,b), Cu (3); R = Me, R' = EtOCO: M = Ni(4), Pd (5), Cu (6); R = MeO, R' = Et, M = Pd (7a,b); R = MeO, R' = EtOCO, M = Pd (8a,b)]. The trifunctionalN,O,O ligands act in all cases as bidentate through the imino and one carbonyl group. Complexes 1-8 are allmonomers with a square planar geometry. Nickel and palladium complexes show more than one form in the solidstate. For example the palladium complex 2 has been synthesized in two forms a and b, which differ in theconformation of the methoxy carbonyl substituent of the chelate ring, while the third isomer or conformer isobtained by thermal treatment at 120 C. Complexes 7 and 8 also exhibit two forms which differ in the degreeof intermolecular hydrogen bonding. Both 7b and 8b crystallize in monoclinic unit cells [7b: space group P21/n,a = 11.963(2), b = 8.438(1), c = 19.637(2) Å, = 94.2(1). 8b: P21/c, a = 10.698(2), b = 14.902(2), c =13.918(2) Å, = 95.2(1)] containing four molecules linked by intermolecular hydrogen bonding [N-H···O=C,2.14-2.36 Å]. All complexes are thermally stable and volatile. Their mass spectra exhibit intense molecular ionpeaks under EI mass conditions.