Yessenia Ocasio-Delgadof, Luis A. Rivera-Riveraf, Gisela Crespo-Romanf, J. E. Cortés-Figueroa
{"title":"Site of Bond Breaking in mer-(Dihapto-[60]fullerene) (Dihapto-1,2-Bis-(DiphenyIphosphino)ethane Tricarbonyl Tungsten(0)","authors":"Yessenia Ocasio-Delgadof, Luis A. Rivera-Riveraf, Gisela Crespo-Romanf, J. E. Cortés-Figueroa","doi":"10.1515/irm-2003-0102","DOIUrl":null,"url":null,"abstract":"Abstract Piperidine (pip) displaces l,2-bis(diphenylphosphino)ethane (dppe) from mer-(η2-C60)(η2-dppe)W(CO)3 to produce mer*-(η2-C60)(η1-ρίρ)2\\ν(ΟΟ)3. The reactions are first order and second order with respect to the molar concentrations of m£r-(r|2-C60)(r|2-dppe)W(CO)3 and pip, respectively. The proposed mechanism, based on the rate law and on the activation parameters, involves an initial pip-assisted ringopening of the dppe ligand to produce the electronically-saturated intermediate fac (η2-C60)(η'-ρίρ) (n1-dppe)W(CO)3. This mechanism differs from previously proposed mechanisms for the ligand exchange reactions of closely-related complexes such as/fac-(η1-L)(η2-dppe)W(CO)3 (L = CO, piperidine, pyridine) and is contrary to the known cis labilizing property of dppe. These results suggest that [60]fullerene has a strong steric influence on the inorganic moiety of the complex and on its chemical behavior.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"88 1","pages":"13 - 20"},"PeriodicalIF":0.0000,"publicationDate":"2003-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"BioInorganic Reaction Mechanisms","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1515/irm-2003-0102","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
Abstract Piperidine (pip) displaces l,2-bis(diphenylphosphino)ethane (dppe) from mer-(η2-C60)(η2-dppe)W(CO)3 to produce mer*-(η2-C60)(η1-ρίρ)2\ν(ΟΟ)3. The reactions are first order and second order with respect to the molar concentrations of m£r-(r|2-C60)(r|2-dppe)W(CO)3 and pip, respectively. The proposed mechanism, based on the rate law and on the activation parameters, involves an initial pip-assisted ringopening of the dppe ligand to produce the electronically-saturated intermediate fac (η2-C60)(η'-ρίρ) (n1-dppe)W(CO)3. This mechanism differs from previously proposed mechanisms for the ligand exchange reactions of closely-related complexes such as/fac-(η1-L)(η2-dppe)W(CO)3 (L = CO, piperidine, pyridine) and is contrary to the known cis labilizing property of dppe. These results suggest that [60]fullerene has a strong steric influence on the inorganic moiety of the complex and on its chemical behavior.
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