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Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds

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Authors
Amor Chico, Francisco JavierUniversity of Alcalá Author; Sánchez-Nieves Fernández, JavierUniversity of Alcalá Author; Royo Gracia, PascualUniversity of Alcalá Author; Jacobsen, Heiko; Blacque, Olivier; [et al.]
Identifiers
Permanent link (URI): http://hdl.handle.net/10017/4200
DOI: 10.1002/1099-0682(200211)2002:11<2810::AID-EJIC2810>3.0.CO;2-C
ISSN: 1099-0682
Publisher
John Wiley & Sons
Date
2002
Affiliation
Universidad de Alcalá. Departamento de Química Inorgánica
Funders
Ministerio de Educación y Ciencia
Bibliographic citation
European Journal of Inorganic Chemistry, 2002, v.2002, n.11, p.2810-2817
Keywords
Tantalum
Competitive insertion
Isocyanide insertion
Density functional calculations
Project
MAT2001-1309 (Ministerio de Ciencia y Tecnología)
info:eu-repo/COST-D12/0016/98
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1002/1099-0682(200211)2002:11<2810::AID-EJIC2810>3.0.CO;2-C
Rights
© Wiley, 2002
Access rights
info:eu-repo/semantics/openAccess
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Abstract
The (amido)methyl complexes [Ta(η5-C5Me5)(NtBu)Me(NR2)] [R = Ph (3), SiMe3 (4)] were prepared by reaction of [Ta(η5-C5Me5)(NtBu)ClMe] (1) with the appropriate lithium amides. Attempts to isolate the analogous NHMe derivative afforded a mixture of complexes [Ta(η5-C5Me5)(NtBu)Me(NHMe)] (5) and [Ta(η5-C5Me5)(NMe)Me(NHtBu)] (6), resulting from hydrogen exchange between the amido and imido ligands. Insertion of CN(2,6-Me2C6H3) into the Ta−Me bond of complexes 3 and 4 gave the η1-iminoacyl derivatives [Ta(η5-C5Me5)(NtBu)(NR2){η1-C(Me)=N(2,6-Me2C6H3)}] [R = Ph (7), SiMe3 (8)], while insertion into the Ta−NRMe (R = H, Me) bond of the complexes [Ta(η5-C5Me5)(NtBu)Me(NRMe)] [R = H (5), Me (2)] gave the η2-iminocarbamoyl compounds [Ta(η5-C5Me5)(NtBu)Me{η2-C(NRMe)=N(2,6-Me2C6H3)}] [R = H (10), Me (9)]. All of the new compounds were characterized by 1H and 13C NMR spectroscopy. The X-ray crystal structure of 9 is reported. DFT calculations were carried out to justify the preference of the insertion either into the Ta−C or the Ta−N bond.
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