Bonding analysis of the neutral electrophilic phosphinidene complexes of vanadium and niobium [(η5-C5H5)(CO)3M(PNR2)] (R = Me, iPr, tBu): A DFT study

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, 31P NMR Spectra, and Reactivities

“…DFT calculations (BP86/TZ2P/ZORA) were also performed on neutral complexes [(η 5 ‐C 5 H 5 )(CO) 3 M(PNR 2 )] (M = V, Nb), with a powerful π‐donor NR 2 adjacent to the phosphinidene P atom. P–M bonds revealed partial double‐bond character and they are rather ionic than covalent . The nature of the M–P bond of M–PNR 2 in cationic complexes [L(CO) 3 M(PNR 2 )] + (M = Co, Rh, Ir, L = PMe 3 , PPh 3 ) was theoretically studied using DFT and DFT–D(3)B methods.…”

Back-Donation in High-Valent d0 Metal Complexes: Does It Exist? The Case of NbV

“…Somehow resembling CO, NHCs are basically not suitable ligands to high-valent metal species . Nevertheless, with reference to high-valent transition-metal (HVTM) halides with the metal in its highest oxidation state (oxidation state of the metal >4, d 0 configuration), a restricted number of NHC complexes have recently been reported and structurally characterized, i.e., [VOCl 3 (IMes)] (IMes = 1,3-dimesitylimidazol-2-ylidene), [NbCl 5 (IPr)] [IPr = 1,3-bis­(2,6-diisopropylphenyl)­imidazol-2-ylidene], [TaBr 5 (IPr)], [TaCl 5 (NHC)], [MCl 4 (NHC) 2 ]­[MCl 6 ] (M = Nb, Ta; NHC = IPr or IMes), [NbOF 3 (IPr)] 2 , and [WO 2 Cl 2 (IPr)] .…”