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New Studies on the Reactivity of Hydride-Containing Niobocene Complexes Towards Insertion and Protonation Processes

2000; Wiley; Volume: 2000; Issue: 7 Linguagem: Inglês

10.1002/1099-0682(200007)2000

1099-0682

Antonío Antiñolo, Fernando Carrillo‐Hermosilla, Juan Fernández‐Baeza, Santiago Garcı́a-Yuste, Antonío Otero, Javier Sánchez-Prada, Elena Villaseñor,

Coordination Chemistry and Organometallics

European Journal of Inorganic ChemistryVolume 2000, Issue 7 p. 1437-1443 Full Paper New Studies on the Reactivity of Hydride-Containing Niobocene Complexes Towards Insertion and Protonation Processes Antonio Antiñolo, Antonio Antiñolo [email protected] Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorFernando Carrillo-Hermosilla, Fernando Carrillo-Hermosilla Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorJuan Fernández-Baeza, Juan Fernández-Baeza Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorSantiago García-Yuste, Santiago García-Yuste Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorAntonio Otero, Antonio Otero Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorJavier Sánchez-Prada, Javier Sánchez-Prada Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorElena Villaseñor, Elena Villaseñor Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this author Antonio Antiñolo, Antonio Antiñolo [email protected] Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorFernando Carrillo-Hermosilla, Fernando Carrillo-Hermosilla Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorJuan Fernández-Baeza, Juan Fernández-Baeza Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorSantiago García-Yuste, Santiago García-Yuste Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorAntonio Otero, Antonio Otero Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorJavier Sánchez-Prada, Javier Sánchez-Prada Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this authorElena Villaseñor, Elena Villaseñor Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain, Fax: (internat.) + 34-926/295-318Search for more papers by this author First published: July 2000 https://doi.org/10.1002/1099-0682(200007)2000:7 3.0.CO;2-JCitations: 17AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract The trihydride complex [Nb(η5-C5H4SiMe3)2(H)3] (1) reacts with diphenylphosphane to afford the monohydride [Nb(η5-C5H4SiMe3)2(H)(PHPh2)] (3). The synthesis of complex 3 has also been achieved from the initial formation of the phosphonium salt [Nb(η5-C5H4SiMe3)2(H)2(PHPh2)]Cl (2) by reaction of the trihydride complex [Nb(η5-C5H4SiMe3)2(H)3] (1) with chlorodiphenylphosphane, followed by deprotonation of this salt in aqueous NaOH. Protonation of complex 3 at low temperature with a slight excess of CF3COOH or CF3COOD leads to the η2-dihydrogen complex [Nb(η5-C5H4SiMe3)2(η2-H2)(PHPh2)]CF3CO2 (4) or its monodeuterated isotopomer [Nb(η5-C5H4SiMe3)2(η2-HD)(PHPh2)]CF3CO2 (5). When the temperature is increased to room temperature, complexes 4 and 5 transform into the transoid dihydrides [Nb(η5-C5H4SiMe3)2(H)2(PHPh2)]CF3CO2 (6) and [Nb(η5-C5H4SiMe3)2(H)2(PDPh2)]CF3CO2 (7), respectively. Complex 3 undergoes an insertion of CS2 into the niobium−hydrogen bond to give the η1-dithioformato complex [Nb(η5-C5H4SiMe3)2(PHPh2)(η1-S-S(S)CH)] (8). This complex could be detected by NMR spectroscopy but could not be isolated due to rapid conversion into the η2-dithioformato complex [Nb(η5-C5H4SiMe3)2(η2-S,S-SSCH)] (9) by loss of the phosphane molecule. Complex 3 also reacts with CO2 to give the η2-formato complex [Nb(η5-C5H4SiMe3)2(η2-O,O-OOCH)] (10); in this case the η1-formato complex could not be detected. The reagent ClPPh2 very smoothly inserts into the Nb−H bond of the complexes [Nb(η5-C5H4SiMe3)2(H)(L)] [L = PHPh2, CN(xylyl), CO; xylyl = 2,6-dimethylphenyl], yielding the new ionic complexes [Nb(η5-C5H4SiMe3)2(PHPh2)(L)]Cl [L = PHPh2 (11), CN(xylyl) (12), CO (13)]. All the complexes described have been characterized by analytical and spectroscopic methods. References [1]G. G. Hlatky, R. H. Crabtree, Coord. Chem. Rev. 1985, 65, 1. 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