N-烷基苯甲酰胺-2,3-二硫醇盐作为聚（二硫醇盐）配体的配位化学研究：1,4-双[(2,3-二巯基苯甲酰胺基)甲基]苯及其与(C₅H₅)Ti片段的螯合物

Coordination Chemistry of N-Alkylbenzamide-2,3-dithiolates as an Approach to Poly(dithiolate) Ligands: 1,4-Bis[(2,3-dimercaptobenzamido)methyl]benzene and Its Chelate Complex with the (C(5)H(5))Ti Fragment.

作者信息

Seidel Wolfram W., Hahn F. Ekkehardt, Lügger Thomas

机构信息

Institut für Anorganische und Analytische Chemie der Freien Universität Berlin, Fabeckstrasse 34-36, D-14195 Berlin, Germany.

出版信息

Inorg Chem. 1998 Dec 28;37(26):6587-6596. doi: 10.1021/ic9706616.

DOI:10.1021/ic9706616

PMID:11670790

Abstract

The bidentate dithiolate ligands N,N-diethyl-2,3-dimercaptobenzamide (H(2)-1), bis(N,N-diethyl-2,3-dimercaptoterephthalamide (H(2)-2), and 1,4-bis(hydroxymethyl)-2,3-dimercaptobenzene (H(4)-3) were synthesized from 2,3-dimercaptobenzoic acid or 2,3-dimercaptoterephthalic acid. The air-sensitive ligands form metallocene complexes of the type [(eta(5)-C(5)H(5))(2)Ti(1)] (13), [(eta(5)-C(5)H(5))(2)Mo(1)] (15), [(eta(5)-C(5)H(5))(2)Ti(3)] (16), and [(eta(5)-C(5)H(5))(2)Ti(2)] (17). Complexes 15 and 16 were characterized by X-ray diffraction. Selected crystallographic details for 15 are as follows: formula C(21)H(23)MoNOS(2); M = 465.49; Pbca; a = 12.536(3), b = 14.313(3), c = 22.463(3) Å; V = 4031(2) Å(3); Z = 8; R = 3.56 and R(w) = 4.49 for 2111 structure factors (F(o)(2) >/= 3sigma(F(o)(2))) and 254 refined parameters. The molybdenum complex 15 shows an almost planar Mo(&mgr;-S)(2)C(2) chelate ring. Selected crystallographic details for 16 are as follows: formula C(18)H(18)O(2)S(2)Ti; M = 378.35; P&onemacr;; a = 10.1778(11), b = 11.5806(14), c = 22.967(3) Å; alpha = 96.42(1), beta = 101.74(1), gamma = 108.82(1) degrees; V = 2462.3(5) Å(3); Z = 6; R = 4.79 and R(w) = 13.27 for 5426 structure factors (I >/= 2sigma(I)) and 766 refined parameters. All titanocene derivatives assume the envelope conformation. The free activation energy for the flip around the S-S axis was determined for 13 to be 69 kJ/mol. The bis(dithiolate) ligand 1,4-bis[(2,3-dimercaptobenzamido)methyl]benzene (H(4)-4) was prepared from 2,3-dimercaptobenzoic acid and converted into the dinuclear air-stable titanocene complex [{(eta(5)-C(5)H(5))(2)Ti}(2)(4)] (19). Complex 19 reacts with HCl/CHCl(3) with liberation of free H(4)-4 while reaction with NMe(4)Cl results in an intramolecular dithiolate shift under formal liberation of [(C(5)H(5))(3)TiCl] and formation of the square-pyramidal chelate complex (NMe(4))[(eta(5)-C(5)H(5))Ti(4)], (NMe(4))[20]. Crystallographic details for (NMe(4))[20].CH(2)Cl(2) are as follows: formula C(32)H(35)Cl(2)N(3)O(2)S(4)Ti; M = 740.67; P&onemacr;; a = 11.579(4), b = 12.210(4), c = 14.016(4) Å; alpha = 112.28(2), beta = 94.46(3), gamma = 104.22(3) degrees; V = 1744.9(10) Å(3); Z = 2; R = 5.35 and R(w) = 12.84 for 2870 structure factors (I >/= 2sigma(I)) and 397 refined parameters. The chelate rings in 20 assume an endo/exo conformation.

摘要

二齿二硫醇盐配体N,N - 二乙基 - 2,3 - 二巯基苯甲酰胺（H₂ - 1）、双（N,N - 二乙基 - 2,3 - 二巯基对苯二甲酰胺）（H₂ - 2）和1,4 - 双（羟甲基） - 2,3 - 二巯基苯（H₄ - 3）由2,3 - 二巯基苯甲酸或2,3 - 二巯基对苯二甲酸合成。这些对空气敏感的配体形成了[(η⁵ - C₅H₅)₂Ti(1)]（13）、[(η⁵ - C₅H₅)₂Mo(1)]（15）、[(η⁵ - C₅H₅)₂Ti(3)]（16）和[(η⁵ - C₅H₅)₂Ti(2)]（17）类型的茂金属配合物。配合物15和16通过X射线衍射进行了表征。15的选定晶体学细节如下：化学式C₂₁H₂₃MoNOS₂；M = 465.49；空间群Pbca；a = 12.536(3)，b = 14.313(3)，c = 22.463(3) Å；V = 4031(2) Å³；Z = 8；对于2111个结构因子（Fₒ² ≥ 3σ(Fₒ²)）和254个精修参数，R = 3.56，R(w) = 4.49。钼配合物15显示出一个几乎平面的Mo(μ - S)₂C₂螯合环。16的选定晶体学细节如下：化学式C₁₈H₁₈O₂S₂Ti；M = 378.35；空间群P1̅；a = 10.1778(11)，b = 11.5806(14)，c = 22.967(3) Å；α = 96.42(1)，β = 101.74(1)，γ = 108.82(1)°；V = 2462.3(5) Å³；Z = 6；对于5426个结构因子（I ≥ 2σ(I)）和766个精修参数，R = 4.79，R(w) = 13.27。所有二茂钛衍生物都呈现信封式构象。13围绕S - S轴翻转的自由活化能测定为69 kJ/mol。双（二硫醇盐）配体1,4 - 双[(2,3 - 二巯基苯甲酰胺基)甲基]苯（H₄ - 4）由2,3 - 二巯基苯甲酸制备，并转化为双核空气稳定的二茂钛配合物[{(η⁵ - C₅H₅)₂Ti}₂(4)]（19）。配合物19与HCl/CHCl₃反应释放出游离的H₄ - 4，而与NMe₄Cl反应则在形式上释放出[(C₅H₅)₃TiCl]并形成四方锥螯合配合物（NMe₄）[(η⁵ - C₅H₅)Ti(4)]，即（NMe₄）[20]。（NMe₄）[20]·CH₂Cl₂的晶体学细节如下：化学式C₃₂H₃₅Cl₂N₃O₂S₄Ti；M = 740.67；空间群P1̅；a = 11.579(4)，b = 12.210(4)，c = 14.016(4) Å；α = 112.28(2)，β = 94.46(3)，γ = 104.22(3)°；V = 1744.9(10) Å³；Z = 2；对于2870个结构因子（I ≥ 2σ(I)）和397个精修参数，R = 5.35，R(w) = 12.84。[20]⁻中的螯合环呈现内/外构象。