首页> 外文期刊>Inorganica Chimica Acta >Complexes of the bis(trimethylsilyl)-benzamidinato ligand 'siam': synthesis and X-ray structures of (siam)(2)M, (siam)(siamH)MX (M = Ni, Pd), (siam)(2)MnI and (siam)ReO3, and their reactivity towards CO2
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Complexes of the bis(trimethylsilyl)-benzamidinato ligand 'siam': synthesis and X-ray structures of (siam)(2)M, (siam)(siamH)MX (M = Ni, Pd), (siam)(2)MnI and (siam)ReO3, and their reactivity towards CO2

机译:双(三甲基甲硅烷基)-苯甲酰胺基配体'siam'的配合物:(siam)(2)M,(siam)(siamH)MX(M = Ni,Pd),(siam)(2)的合成和X射线结构MnI和(siam)ReO3及其对CO2的反应性

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Complexes with the bis(trimethylsilyl)-benzamidinato ligand 'siam' of the type (siam)(2)M (M=Ni (2), Pd (3)), (siam)(siamH)NiBr (4a), (siam)(siamH)PdCl (4b) and (siam)(2)MnI (5) were prepared by reaction of (siam)(2)Mg(thf)(2) (1) with the corresponding metal halides and addition of water or iodine, respectively. The reaction of (siam)(2)Zn with Re2O7 yielded (siam)ReO3 (6). X-ray analysis of 1-6 revealed that siam acts as a bidentate ligand forming four-membered chelate rings in all complexes. In 2 four nitrogen atoms show a distorted tetrahedron; in contrast, 3, 4a and 4b are square planar complexes. In both 4a and 4b siamH is coordinated as a monodentate ligand. The Mn(III) complex 5 exhibits a trigonal bipyramidal coordination of the four amidinato nitrogens and the iodo ligand, which occupies an equatorial position. The Re(VII) complex 6 shows an irregular trigonal bipyramidal coordination. In all compounds the bond lengths and angles in the amidinato ligand are comparable and exhibit typical values. The reaction of 2 with excess CO2 gave a green dimeric complex 7 in which one Ni(II) centre is octahedral and the other is square pyramidal coordinated. X-ray analysis revealed that 5 mol CO2 per 2 mol nickel are inserted in N-Si bonds forming new types of tridentate bridging ligands which contain N-COOSiMe3 groups. (C) 1998 Elsevier Science S.A. All rights reserved. [References: 26]
机译:与(siam)(2)M(M = Ni(2),Pd(3)),(siam)(siamH)NiBr(4a),(siam)类型的双(三甲基甲硅烷基)-苯甲酰胺基配体'siam'的配合物)(siamH)PdCl(4b)和(siam)(2)MnI(5)是通过(siam)(2)Mg(thf)(2)(1)与相应的金属卤化物反应并加水或碘。 (siam)(2)Zn与Re2O7的反应生成(siam)ReO3(6)。 X射线分析1-6显示,siam充当双齿配体,在所有复合物中形成四元螯合环。在2中,四个氮原子显示出扭曲的四面体;相反,3、4a和4b是方形平面络合物。在4a和4b中,siamH均被配制成单齿配体。 Mn(III)配合物5表现出四个a胺氮原子和碘配体的三角双锥体配位,其占据赤道位置。 Re(VII)络合物6显示不规则的三角双锥体配位。在所有化合物中,酰胺基配体中的键长和键角均相当,并具有典型值。 2与过量CO2的反应生成绿色二聚体配合物7,其中一个Ni(II)中心为八面体,另一个为方角锥体配位。 X射线分析表明,每2摩尔镍中有5摩尔CO2插入N-Si键中,形成了新型的三齿桥接配体,其中含有N-COOSiMe3基团。 (C)1998 Elsevier Science S.A.保留所有权利。 [参考:26]

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