Hydride Transfer Reactivity of Mo(L)(H)(depe)₂ (L = N, NBEt₃)

Abstract

Starting from Mo(N 2 ) 2 (depe) 2 (1), the nitrido complex Mo(N)-(N 3 )(depe) 2 (2) was obtained by the reaction of 1 with Me 3 -SiN 3 . Subsequent reaction of 2 with HCl in CH 3 OH afforded the cationic imido chloride 3, which could be converted into the nitrido chloride 4 with sodium bis(trimethylsilyl)amide. From 3 and 4 the hydrido complexes of the type Mo(H)(L)-(depe) 2 [L = N (7), NBEt 3 (8)] were obtained by the reaction with the hydride reagents LiBH 4 and NaHBEt 3 . The hydridic character of the L n M-H bond of 8 was determined by DQCC measurements (bond ionicity i = 81 %). Hydride reactivity studies were carried out on 7 and 8; however, only 8 underwent hydride transfer reactions. 8 reacted with 4,4Ј-dichlorobenzophenone and acetophenone to afford the correspond-

Dinitrogen‐Molybdenum Complex Induces Dinitrogen Cleavage by One‐Electron Oxidation

“…2.45 Å) . Although a similar molybdenum(IV) nitride complex, [Mo(N)(Cl)(depe) 2 ], has been prepared by using azide reagents, as reported by Berke and co‐workers, 2 is the first example of the five‐coordinate Mo IV nitride complex, supported by a depe ligand, resulting from N 2 cleavage.…”

Molybdenum dinitrogen complexes supported by a silicon-centred tripod ligand and dppm or dmpm: tuning the activation of N2

“…Samples were burned in sealed tin containers in a stream of oxygen. Spectroscopic characterization 1 H, 13 C, 29 Si and 31 P NMR spectra were recorded at 300 K with a Bruker AVANCE 400 Pulse FT spectrometer and referenced either to the solvent residual signal (CH 2 Cl 2 = 5.32 ppm, C 6 D 6 = 7.16 ppm) or to TMS (δ 1H = 0 ppm) and 85% H 3 PO 4 (δ 31P = 0 ppm) as substitutive standards. Spectral simulations were performed using the MestReC program package (MestreLab Research, Santiago de Compostella, Spain).…”

A quantitative measure of the ionicity of selected iron hydride species by examination of the deuterium quadrupole coupling constant (DQCC)

“…The mechanism of exchange, may involve the loss of phosphine arm to form a 5-coordinate iron centre, how- [32] ever, this has not been established unequivocally [21]. T 1 measurements in the 2 H NMR spectrum at temperatures close to coalescence were not attempted as the observed resonances were too broad.…”