The nature of the bridging nitrido ligand. Synthesis and reactivity of heterobimetallic nitrido-bridged compounds

Autor:	Carolyn M. Jones, Nancy M. Doherty
Rok vydání:	1995
Předmět:	chemistry.chemical_classification Hydride Cationic polymerization chemistry.chemical_element Condensation reaction Medicinal chemistry Oxidative addition Rhodium Adduct Inorganic Chemistry chemistry Materials Chemistry Organic chemistry Iridium Physical and Theoretical Chemistry Bridged compounds
Zdroj:	Polyhedron. 14:81-91
ISSN:	0277-5387
DOI:	10.1016/0277-5387(94)00355-i
Popis:	Heterobimetallic nitrido-bridged compounds (R 3 SiO) 3 VNM(CO)(PPh 3 ) 2 (R  Me or Et and M  Ir or Rh) and (Me 3 SiO) 3 VNRh(PPh 3 ) 3 have been synthesized by condensation reactions between vanadium silylimido compounds, V(NSiR 3 )(OSiR 3 ) 3 , and group VIII metal fluorides, MF(L)(PPh 3 ) 2 . Oxidative addition of small molecules (MeI, O 2 , H 2 ) to the iridium(I) of (R 3 SiO) 3 VNIr(CO)(PPh 3 ) 2 occurs, producing iridium(III) compounds in which the VNIr interaction is retained. In contrast, however, the nitrido linkages in (Me 3 SiO) 3 VNM(L)(PPh 3 ) 2 are readily cleaved by silylating reagents (ClSiMe 3 , ClSiEt 3 , HSiEt 3 ), producing V(NSiR 3 )(OSiMe 3 ) 3 and a group VIII metal chloride or hydride product. Comparison of the reactivity and spectroscopic data among the nitrido-bridged compounds and with related iridium(I) and rhodium(I) complexes suggests that the nitrido-bridged compounds are best viewed as adducts in which anionic [(R 3 SiO) 3 VN:] − acts as a simple two-electron donor to the 14-electron cationic [M(L)(PPh) 2 ] + fragment.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::ee5f0f9a594b5f77fe881042dba833e4 https://doi.org/10.1016/0277-5387(94)00355-i Zobrazit plný text záznamu Full Text from ScienceDirect