A Nitrido Salt Reagent of Titanium

Abstract

Deprotonation of the parent titanium imido ((tBu)nacnac)Ti≡NH(Ntolyl2) ((tBu)nacnac(-) = [ArNC(t)Bu]2CH; Ar = 2,6-(i)Pr2C6H3) with KCH2Ph forms a rare example of a molecular titanium nitride as a dimer, {[K][((tBu)nacnac)Ti≡N(Ntolyl2)]}2. From the parent imido or nitride salt, the corresponding aluminylimido-etherate adduct, ((tBu)nacnac)Ti≡N[AlMe2(OEt2)](Ntolyl2), can be isolated and structurally characterized. The parent imido is also a source for the related borylimido, ((tBu)nacnac)Ti═NBEt2(Ntolyl2).

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

“…In this work, we have found new and reliable methods to a wide family of terminal uranium nitrides based on the U(Tren TIPS ) framework (Supplementary Note 2), and it is our hope that this could be applicable to other ligand systems. We note that the reactivity described here is analogous to that reported recently for a titanium nitride59, since uranium is behaving like an early d -block ion in this context.…”

Molecular titanium nitrides: nucleophiles unleashed

“…42–51 Thus, we focused our attention on group 4, especially on Ti, since reactivity studies of mononuclear nitrides in this group have largely evaded the reach of the synthetic chemist until recently. 52,53 The fact that mononuclear titanium nitrides are exceedingly rare is rather surprising since group 4 nitrides have been proposed in N 2 activation and reductive splitting reactions, and the nitride group is often generated in route to the deposition of thin metal nitride films. The elusive nature of terminal titanium nitrides, adjunct with the wealth of useful reactivity established in mid-transition metal nitrides, calls for the attention to probe the nature of this highly polarized bond and to determine the degree of nucleophilicity in this rather uncharacterized motif.…”

“…2). 52 However, due to degradation in this ligand scaffold, as well as other decomposition pathways, reactivity studies of this system were quite restricted. We turned instead to new titanium nitrides supported by two PN – ligands (PN – = N -(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide, Fig.…”

Mononuclear and Terminally Bound Titanium Nitrides

“…These distances are comparable to a similar species recently described by our group, namely [K] 2 [( tBu nacnac)TiN(Ntolyl 2 )] 2 . 18 Unlike the latter species, however, complex 3 does not exhibit any K + ···arene interactions, but instead, the K + ions adopt a three-coordinate and planar geometry as the result of each interacting to both nitrides and one Et 2 O molecule. The K and N nitride atoms form a planar diamond core (sum of four angles = 360°), while the geometry at the Ti centers is intermediate between square pyramidal and trigonal bipyramidal (τ = 0.52).…”

“…To circumvent the vulnerability of the β-diketiminate ligand, we resorted to a more robust monoanionic chelating ligand PN − (PN − = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) 19 as well as explored a more direct route to this reactive functional group without the need to generate transient nitridyl species, which abstracted H• to form the parent imido [( tBu nacnac)Ti≡NH(Ntolyl 2 )]. 18 Herein, we introduce a convenient entry to dinuclear and mononuclear titanium nitride complexes, as well as the isolation of the first discrete salt of titanium having a terminally bound nitride ligand.When TiCl 3 (THF) 3 is treated with 2 equiv of LiPN in toluene, complex (PN) 2 TiCl (1) is formed in 75% yield as orange-brown crystals (Scheme 1). Consistent with a paramagnetic, d 1 complex, the 1 H NMR spectrum of 1 features broadened chemical shifts ranging from 12 to −6 ppm, and no signal for the PN ligand is observable in the 31 P{ 1 H} NMR spectrum.…”