A New Side‐on End‐On Ditantalum Dinitrogen Complex and Its Reaction with BuSiH₃

Abstract

The formation of the P-cyclohexyl dinitrogen complex,= [CyP(CH 2 SiMe 2 NPh) 2 ], and Cy = C 6 H 11 ) is described and its reaction with butylsilane (BuSiH 3 ) explored. The reaction was monitored by multinuclear NMR spectroscopy and showed the formation of a

Dinitrogen activation by group 4 and group 5 metal complexes supported by phosphine-amido containing ligand manifolds

“…When this was attempted, we were able to isolate a material with the P-phenyl group cyclometalated, and the two silylimide units rearranged to generate a disilylamido-silylimido unit (15.4) (Scheme 15) [67]. Modification of NPN Si to include P-cyclohexyl as a replacement for the P-phenyl substituents was examined in order to avoid the P-phenyl cyclometalation and ideally push the reaction forward to the desired outcome of tris(butylsilyl)amine elimination [75]. The P- We were also interested in examining the reactions of neutral group 13 Lewis acids and 13.3.…”

Nitrogen Fixation via Splitting into Nitrido Complexes

“…Reaction of the ditantalum complex [(μ-H) 4 {Ta­(NPN)} 2 ] (NPN = PhP­(CH 2 SiMe 2 NPh) 2 ) with N 2 gave [(μ-η 2 -η 1 -N 2 )­(μ-H) 2 {Ta­(NPN)} 2 ] as the first example of the rare end-on/side-on binding mode with highly activated N 2 (Scheme ). Subsequent treatment of the N 2 complex with boranes, silanes, − aluminum or zirconium hydrides, , or 1,2-cumulenes enabled full cleavage of the N 2 bond.…”

Reactivity and Structure of Complexes of Small Molecules: Dinitrogen

“…In 2015, the same group developed a similar complex with the [NP Cy N] ligand. 120 A wealth of reactivity has been discovered with this complex. 121 , Focusing on the reactivity of the bridging NN, the nucleophilic character of the "terminal" N is evidenced first by reaction with electrophiles such as PhCH 2 Br 113 or X=C=X' ( X, X' = S or NPh).…”