Reaction of Tp(PPh3)Ru(η2-O2CCHPh2) with carbene and vinylidene precursors

被引：26

作者：

Sanford, MS ^{[1
]}

Valdez, MR ^{[1
]}

Grubbs, RH ^{[1
]}

机构：

[1] CALTECH, Arnold & Mabel Beckman Labs Chem Synthesis, Div Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 25期

关键词：

D O I：

10.1021/om010558v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Tp(PPh3)Ru(eta (2)-O2CCHPh2) (1) [Tp = tris(pyrazolyl)borate] has been prepared by the reaction of TpRu(Cl)(PPh3)(2) with 1.2 equiv of NaO2CCHPh2. Complex 1 reacts with diphenylcyclopropene to generate the metallacycle Tp(PPh3)Ru[kappa (2)-(C,O)-C(double bond CHCHPh2)OC(CHPh2)double bondO] (2). A trace of the carbene Tp(PPh3)(eta (1)-O2CCHPh2)Ru double bond CHCH double bondC(Ph)(2) (3) is also observed in the crude reaction mixture. Compound I reacts with phenyldiazomethane to form the benzylidene Tp(PPh3)(eta (1)-O2CCHPh2)Ru double bond CHPh (4). A similar species is also available by the reaction between AgO2CCHPh2 and Tp(PCy3)(Cl)Ru double bond CHCH double bondC(CH3)(2) (5), which affords Tp(PCy3)(eta (1)-O2CCHPh2)Ru double bond CHCH double bondC(CH3)(2) (6). With the addition of an excess of HCl, complexes 4 and 6 release free HO2CCHPh2 and are converted to Tp(PPh3)(Cl)Ru double bond CHPh (7) and complex 5, respectively. The reaction of I with phenylacetylene yields the five-membered chelate TP(PPh3)Ru[kappa (2)-(C,O)-C(double bond CHPh)OC(CHPh2)double bondO] (8). Complex 8 is also formed in the reaction of Tp(PPh3)(Cl)Ru double bondC double bond CHPh with 1.2 equiv of AgO2CCHPh2. Compounds 1, 2, and 8 have been characterized by X-ray crystallography. Complexes 2, 5, 6, 7, and 8 do not catalyze olefin metathesis reactions, while 4 is an active initiator for the ring-opening metathesis polymerization of norbornene.

引用

页码：5455 / 5463

页数：9

共 60 条

[31] Synthesis and reactivity of neutral vinylidene and σ-alkynyl complexes containing the hemilabile ligand Ph2PCH2CH2OMe -: Part 16.: Ruthenium tris(pyrazolyl)borate complexes [J].