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Stepwise formation of quasi-octahedral macrocyclic complexes of rhodium(II) and iridium(III) bearing a pentamethylcyclopentadienyl group

机译:逐步形成带有五甲基环戊二烯基的铑(II)和铱(III)的准八面体大环配合物

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摘要

Reactions of [{MCl_2(Cp~*)}_2] (1: M = Ir, 2: M = Rh) with bidentate ligands (L) such as 1,4-diisocyano-2,5-dimethylbenzene (a), 1,4-diisocyano-2,3,5,6-tetramethylbenzene (b), pyrazine (c) or 4,4'-dipyridyl (d) gave the corresponding dinuclear complexes [{MCl_2(Cp~*)}_2 (L)] (M = Ir; 3a, 3b, 5c, 5d; M=Rh: 4b,6c, 6d), which were converted into tetranuclear complexes [{M_2(#mu#-Cl)_2(Cp~*)_2}_2(L)_2](OTf)_4 (M = Ir: 7c, 7d, 9a, 9b: M = Rh: 8c, 8d, 10b) on treatment with Ag(OTf). X-ray analyses of 8c and 8d revealed that each of four pentamethylcyclopentadieny metal moieties was connected by two #mu#-Cl-bridged atoms and a bidentate ligand to construct a rectangular cavity with the dimensions of 3.7 X 7.0 A for 8c and 3.7 X 11.5 A for 8d. Both the Rh-2Cl_2 and pyrazine (for 4,4' dipyridyl) ring planes are perpendicular to the Rh_4 plane. Treatment of Cl-bridged complexes (7c, 7d, 8c, 8d, 9b, and 10b) with a different ligand (L') resulted in cleavage of the Cl bridges too produce two-dimensional complexes [{MCl(Cp~*)}_4{(L)(L')}_2](OTf)_4 (11ac, 11bc, 11bd, 12bc, and 12bd) with two different ligand "edges". Complex 10b reacted readily with 1,4-diisocyano-2,3,5,6-tetramethylbenzene (b) to give a tetranuclear rhodium(II) complex 12bb. The structure of tetranuclear complexes was confirmed by X-ray analysis of 11bc. Each {MCp~*} moiety is surrounded by a Cl atom, isocyanide, and pyrazine (or 4,4'-dipyridyl) and the dimensions of its cavity are 7.0 X 11.6 A.
机译:[{MCl_2(Cp〜*)} _ 2](1:M = Ir,2:M = Rh)与双齿配体(L)如1,4-二异氰基-2,5-二甲基苯(a),1的反应,4-二异氰基-2,3,5,6-四甲基苯(b),吡嗪(c)或4,4'-二吡啶基(d)得到相应的双核配合物[{MCl_2(Cp〜*)} _ 2(L) ](M = Ir; 3a,3b,5c,5d; M = Rh:4b,6c,6d),它们被转化为四核配合物[{M_2(#mu#-Cl)_2(Cp〜*)_ 2} _2 (L)_2](OTf)_4(M = Ir:7c,7d,9a,9b:M = Rh:8c,8d,10b),用Ag(OTf)处理。对8c和8d的X射线分析表明,四个五甲基环戊二烯金属部分分别通过两个#mu#-Cl桥联原子和一个双齿配体相连,以构建一个矩形腔,其大小分别为3.7 X 7.0 A(对于8c和3.7 X 11.5 A,持续8d。 Rh-2Cl_2和吡嗪(对于4,4'二吡啶基)环平面均垂直于Rh_4平面。用不同的配体(L')处理Cl桥连络合物(7c,7d,8c,8d,9b和10b)导致Cl桥的裂解也产生了二维络合物[{MCl(Cp〜*)} _4 {(L)(L')} _ 2](OTf)_4(11ac,11bc,11bd,12bc和12bd),带有两个不同的配体“边缘”。配合物10b容易与1,4-二异氰基-2,3,5,6-四甲基苯(b)反应,得到四核铑(II)配合物12bb。通过11bc的X射线分析证实了四核复合物的结构。每个{MCp〜*}部分均被Cl原子,异氰化物和吡嗪(或4,4'-二吡啶基)包围,并且其空腔尺寸为7.0 X 11.6A。

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