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首页> 外文期刊>Journal of Organometallic Chemistry >Syntheses and structures of di- and trinuclear heterometallic complexes with nitrido bridges between rhenium and titanium
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Syntheses and structures of di- and trinuclear heterometallic complexes with nitrido bridges between rhenium and titanium

机译:-和钛之间具有亚硝基桥的二核和三核异金属配合物的合成和结构

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摘要

[TiCl_4(MeCN)]_2 (1) is obtained from a gas phase reaction of TiCl_4 and MeCN. It crystallizes in the orthorhombic space group Cmca with the cell constants a=961.8(2), b=984.0(5), c=1637.0(4) pm. and Z = 4. The symmetry of the dinuclear complex is C_(2h). The Ti atoms are connected with symmetrical chloro bridges, and the octahedral coordination is completed by one acetonitrile ligand coordinated to each Ti atom. [TiCL_4(MeCN)]_2 reacts with ReNCl_2(PMe_2Ph)_3 in CH_2Cl_2 to form the dinuclear complex (Me_2PhP)_3(MeCN)ClRe≡N-TiCl_5 (2). It crystallizes as 2(centre dot)CH_2Cl_2 in the monoclinic space group P2_1 with the cell constants a =982.0(2), b = 1245.3(2),c = 3088.1 (5) pm, β = 92.44(2), and Z = 4. The linear nitrido bridge (Re-N-Ti = 167.7(4)) is characterized by distances Re-N = 167.8(8) pm and Ti-N = 223.9(9) pm. By using a fourfold excess of ReNCl_2(PMe_2Ph)_3 in toluene, the trinuclear complex [(Me_2PhP)_3Cl_2ReN]_2 TiCl_4 (3) is obtained in form of crystals 3(centre dot)2 toluene: P1, a = 1070.4(2), b = 1283.2(5), C = 1300.0(3) pm, α = 85.21(2), β = 80.57(2), γ=86.19(3), Z = 1. The centrosymmetric complex 3 contains a linear axis Re≡N-Ti-N≡Re with a Re-N distance of 168.5(9) pm and a Ti-N distance of 215.7(9) pm.
机译:[TiCl_4(MeCN)] _ 2(1)由TiCl_4与MeCN的气相反应制得。它在正交常数空间群Cmca中结晶,晶格常数为a = 961.8(2),b = 984.0(5),c = 1637.0(4)pm。 Z =4。双核配合物的对称性为C_(2h)。 Ti原子与对称的氯桥相连,八面体配位由一个与每个Ti原子配位的乙腈配体完成。 [TiCL_4(MeCN)] _ 2与CH_2Cl_2中的ReNCl_2(PMe_2Ph)_3反应形成双核络合物(Me_2PhP)_3(MeCN)ClRe≡N-TiCl_5(2)。在单斜空间群P2_1 / n中以2个中心点CH_2Cl_2结晶,其单元常数a = 982.0(2),b = 1245.3(2),c = 3088.1(5)pm,β= 92.44(2), Z =4。线性氮化桥(Re-N-Ti = 167.7(4))的特征是距离Re-N = 167.8(8)pm和Ti-N = 223.9(9)pm。通过在甲苯中使用四倍过量的ReNCl_2(PMe_2Ph)_3,可以得到晶体3(中心点)2甲苯形式的三核配合物[(Me_2PhP)_3Cl_2ReN] _2 TiCl_4(3):P1,a = 1070.4(2) ,b = 1283.2(5),C = 1300.0(3)pm,α= 85.21(2),β= 80.57(2),γ= 86.19(3),Z =1。中心对称复合物3包含一个线性轴Re ≡N-Ti-N≡Re,Re-N距离为168.5(9)pm,Ti-N距离为215.7(9)pm。

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