| 12639155 |
Cunha SM, Guedes da Silva MF, Pombeiro AJ: Mixed dinitrogen-organocyanamide complexes of molybdenum (0) and their protic conversion into hydrazide and amidoazavinylidene derivatives. Inorg Chem. 2003 Mar 24;42(6):2157-64.
Organocyanamides, Ntbd1;CNR (2) (R = Me or Et), react with trans-[Mo (N (2))(2)(dppe)(2)] (1, dppe = Ph (2) PCH (2) CH (2) PPh (2)), in THF, to give the first mixed molybdenum dinitrogen-cyanamide complexes trans-[Mo (N (2))(NCNR (2))(dppe)(2)] (R = Me 2a or Et 2b) which are selectively protonated at N (2) by HBF (4) to yield the hydrazide (2-) complexes trans-[Mo (NNH (2))(NCNR (2))(dppe)(2)][BF (4)](2) (R = Me, 3a, or Et, 3b). On treatment with Ag [BF (4)], oxidation and metal fluorination occur, and the ligating cyanamide undergoes an unprecedented beta-protonation at the unsaturated C atom to form trans-[MoF (NCHNR (2))(dppe)(2)][BF (4)](2) (R = Me, 4a, or Et, 4b) compounds which present the novel amidoazavinylidene (or amidomethyleneamide) ligands. Complexes 4 are also formed from the corresponding compounds 3, with liberation of ammonia and hydrazine. The crystal structure of 2b was determined by single-crystal X-ray diffraction analysis which indicates that the N atom of the amide group has a trigonal planar geometry. |
31(0,1,1,1) |