RT info:eu-repo/semantics/article
T1 Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds
A1 Amor Chico, Francisco Javier
A1 Sánchez-Nieves Fernández, Javier
A1 Royo Gracia, Pascual
A1 Jacobsen, Heiko
A1 Blacque, Olivier
A1 Berke, Heinz
A1 Lanfranchi, Maurizio
A1 Pellinghelli, Maria Angela
A1 Tiripicchio, Antonio
K1 Tantalum
K1 Competitive insertion
K1 Isocyanide insertion
K1 Density functional calculations
K1 Ciencia
K1 Química inorgánica
K1 Science
K1 Chemistry, inorganic
AB 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.
PB John Wiley & Sons
SN 1099-0682
YR 2002
FD 2002
LK http://hdl.handle.net/10017/4200
UL http://hdl.handle.net/10017/4200
LA eng
NO Ministerio de Educación y Ciencia
DS MINDS@UW
RD 20-abr-2024