含嘧啶 - 2 - 硫醇盐（pymS）配体的铼和锰四核方形配合物的合成、结构与反应活性：含M(CO)(3)（M = Re, Mn）片段的单核和多核化合物的通用高效前体

Synthesis, structure and reactivity of tetranuclear square-type complexes of rhenium and manganese bearing pyrimidine-2-thiolate (pymS) ligands: versatile and efficient precursors for mono- and polynuclear compounds containing M(CO)(3) (M = Re, Mn) fragments.

作者信息

Kabir S E, Alam J, Ghosh S, Kundu K, Hogarth G, Tocher D A, Hossain G M G, Roesky H W

机构信息

Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh.

出版信息

Dalton Trans. 2009 Jun 21(23):4458-67. doi: 10.1039/b815337j. Epub 2009 Apr 14.

DOI:10.1039/b815337j

PMID:19488443

Abstract

Reactions of M(2)(CO)(10) (M = Re, Mn) with pyrimidine-2-thiol (pymSH) in the presence of Me(3)NO afford the tetranuclear square-type complexes [M(4)(CO)(12)(micro-kappa(3)-pymS)(4)] (, M = Re; , M = Mn). Both consist of four M(CO)(3) (M = Re, Mn) units, pairs of which are joined by tridentate pyrimidine-2-thiolate ligands. Treatment of with a variety of donor ligands results in cleavage of the square to afford mononuclear species with either a mono- or bidentate pyrimidine-2-thiolate ligand. Triphenylphosphine reacts with to give [Mn(CO)(3)(PPh(3))(kappa(2)-pymS)] () in which the pyrimidine-2-thiolate coordinates in a bidentate fashion. With diamines [M(CO)(3)(kappa(2)-L)(kappa(1)-pymS)] () (M = Re, Mn; L = 2,2'- bipy, 1,10-phen, en) result in which the pyrimidine-2-thiolate binds in a monodentate fashion through sulfur. With diphosphines, complexes with different stoichiometries and pyrimidine-2-thiolate binding modes are obtained depending on the nature of the metal and diphosphine. With dppm and dppe, gives [Re(CO)(2)(kappa(1)-pymS)(kappa(2)-dppm)] () and [Re(CO)(2)(kappa(2)-pymS)(kappa(1)-dppe)(2)] (), respectively, whereas affords [Mn(CO)(2)(kappa(2)-pymS)(kappa(1)-dppm)(2)] () and [Mn(CO)(2)(kappa(2)-pyS)(kappa(2)-dppe)] () under similar conditions. Reactions of with [Os(3)(CO)(10)(NCMe)(2)] affords mixed-metal butterfly clusters [MOs(3)(CO)(13)(micro(3)-kappa(2)-pymS)] () in which the group 7 metal occupies a wing-tip position and the pyrimidine-2-thiolate ligand caps a triangular Os(2)M face. With Ru(3)(CO)(12), carbon-sulfur bond cleavage occurs to give the tetranuclear clusters [MRu(3)(CO)(14)(micro(4)-S)(micro-kappa(1):eta(1)-pym)] () bearing both the extruded sulfur and the heterocyclic ring. The molecular structures of , and have been established by X-ray diffraction allowing the binding mode of the pyrimidine-2-thiolate ligands to be probed.

摘要

在三甲基硝酸酯存在下，M(2)(CO)(10)（M = Re、Mn）与嘧啶 - 2 - 硫醇（pymSH）反应生成四核方形配合物[M(4)(CO)(12)(μ - κ(3)-pymS)(4)]（，M = Re；，M = Mn）。两者均由四个M(CO)(3)（M = Re、Mn）单元组成，其中成对的单元通过三齿嘧啶 - 2 - 硫醇盐配体相连。用各种供体配体处理会导致方形结构裂解，生成具有单齿或双齿嘧啶 - 2 - 硫醇盐配体的单核物种。三苯基膦与反应生成[Mn(CO)(3)(PPh(3))(κ(2)-pymS)]（），其中嘧啶 - 2 - 硫醇盐以双齿方式配位。与二胺反应生成[M(CO)(3)(κ(2)-L)(κ(1)-pymS)]（）（M = Re、Mn；L = 2,2'-联吡啶、1,10 - 菲咯啉、乙二胺），其中嘧啶 - 2 - 硫醇盐通过硫以单齿方式结合。与二膦反应，根据金属和二膦的性质得到不同化学计量比和嘧啶 - 2 - 硫醇盐结合模式的配合物。与dppm和dppe反应，分别生成[Re(CO)(2)(κ(1)-pymS)(κ(2)-dppm)]（）和[Re(CO)(2)(κ(2)-pymS)(κ(1)-dppe)(2)]（），而在类似条件下生成[Mn(CO)(2)(κ(2)-pymS)(κ(1)-dppm)(2)]（）和[Mn(CO)(2)(κ(2)-pyS)(κ(2)-dppe)]（）。与[Os(3)(CO)(10)(NCMe)(2)]反应生成混合金属蝴蝶簇[MOs(3)(CO)(13)(μ(3)-κ(2)-pymS)]（），其中第7族金属占据翼尖位置，嘧啶 - 2 - 硫醇盐配体覆盖三角形Os(2)M面。与Ru(3)(CO)(12)反应，发生碳 - 硫键裂解，生成四核簇[MRu(3)(CO)(14)(μ(4)-S)(μ - κ(1):η(1)-pym)]（），其中既有挤出的硫又有杂环。通过X射线衍射确定了、和的分子结构，从而能够探究嘧啶 - 2 - 硫醇盐配体的结合模式。