Lehtonen Ari, Sillanpää Reijo
Department of Chemistry, University of Turku, FIN-20014 Turku, Finland.
Inorg Chem. 2004 Oct 4;43(20):6501-6. doi: 10.1021/ic049448h.
The reaction between trisdiolatotungsten(VI) complex [W(eg)(3)] (1) (eg = 1,2-ethanediolato dianion) and phenolic ligand precursor methylamino-N,N-bis(2-methylene-4,6-dimethylphenol) (H(2)L(Me)) or methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol) (H(2)L(tBu)) affords monomeric oxotungsten complex [WO(eg)(L(Me))] (2) or [WO(eg)(L(tBu))] (3), respectively. These complexes react further with chlorinating reagents, which leads to the displacement of ethanediolato ligands from the complex units and formation of cis and trans isomers of the corresponding dichloro complexes [WOCl(2)(L(Me))] (4) and [WOCl(2)(L(tBu))] (5), respectively. Identical dichloro complexes were also prepared by the reaction between the above-mentioned phenolic ligand precursors and [WOCl(4)]. Molecular structures of 3, cis-4, trans-4, and cis-5 were verified by X-ray crystallography. Complexes 2-5 can be activated by Et(2)AlCl to catalyze ring-opening metathesis polymerization of norbornene.
三二醇合钨(VI)配合物[W(eg)(3)](1)(eg = 1,2 - 乙二醇二价阴离子)与酚类配体前体甲氨基 - N,N - 双(2 - 亚甲基 - 4,6 - 二甲基苯酚)(H(2)L(Me))或甲氨基 - N,N - 双(2 - 亚甲基 - 4 - 甲基 - 6 - 叔丁基苯酚)(H(2)L(tBu))反应,分别生成单体氧钨配合物[WO(eg)(L(Me))](2)或[WO(eg)(L(tBu))](3)。这些配合物进一步与氯化试剂反应,导致乙二醇酸酯配体从配合物单元中被取代,并分别形成相应二氯配合物[WOCl(2)(L(Me))](4)和[WOCl(2)(L(tBu))](5)的顺式和反式异构体。通过上述酚类配体前体与[WOCl(4)]的反应也制备了相同的二氯配合物。通过X射线晶体学确定了3、顺式 - 4、反式 - 4和顺式 - 5的分子结构。配合物2 - 5可被Et(2)AlCl活化以催化降冰片烯的开环易位聚合反应。