Townsend Erik M, Hyvl Jakub, Forrest William P, Schrock Richard R, Müller Peter, Hoveyda Amir H
Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Organometallics. 2014 Oct 13;33(19):5334-5341. doi: 10.1021/om500655n. Epub 2014 Sep 22.
Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-PhCH (STPP) and S-2,6-(mesityl)CH (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was -selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes.
已制备了含有S-2,3,5,6-PhCH(STPP)和S-2,6-(均三甲苯基)CH(SHMT = S-六甲基三联苯)类型苯硫酚盐配体的钼和钨的亚胺基亚烷基配合物以及钨的氧代亚烷基配合物，以便将它们的复分解活性与类似的酚盐配合物的复分解活性进行比较。对于1-辛烯的复分解均偶联或2,3-二碳甲氧基降冰片烯的聚合反应，所有硫醇盐配合物的反应速度都明显较慢（慢至约10倍），并且它们都没有选择性。反应速度较慢可归因于苯硫酚盐相对于类似酚盐具有更强的σ供电子能力，因此苯硫酚盐配合物中金属处的电子密度更高。
