Activation of the strongest triplet bond in molecular nitrogen (N2) under mild conditions is particularly challenging. Recently, its fixation and reduction were achieved by highly reactive dicoordinated borylene species at ambient conditions, ripping the limits of harsh reaction conditions by metallic species. Less reactive species with a facile preparation could be desirable for next-generation N2 activation. Now density functional theory calculations reveal that tricoordinated boranes could be a potential candidate of N2 activation/functionalization.

Density functional theory calculations were used to investigate the reaction mechanisms on [3 + 2] cycloaddition reactions of azides with metal carbyne complexes. Our results reveal that the formation of a 1,4-metallatriazole regioisomer is a kinetically favorable process in comparison with the formation of 1,5-metallatriazole. Aromaticity plays an important role in stabilizing the products in these reactions. Further analyses show that the electron-donating ligand on metal centers or the electron-withdrawing group on the azide could accelerate the [3 + 2] cycloaddition reaction.

Treatment of [Ir(PPh3)3Cl] with 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine (Hdpp) in refluxing toluene affords an unexpected pyrrole-metalated iridium(III) hydride complex, [Ir(K2C,N-dpp)(H)(Cl)(PPh3)2] (1), via Cpyrrole–H activation, while the presence of the base KOtBu as the deprotonation reagent produces a pyridine-metalated iridium(III) hydride complex, [Ir(K3C,N,N-dpp)(H)(PPh3)2] (2), via Cpyridine–H activation.

A series of phosphorus-substituted germanium(II) complexes, L1GeR [L1 = CH{(CMe)(2,6-iPr2C6H3N)}2; 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph2; 5b, R = OP(O) (OnBu)2; 6a, R = OP(S)Ph2; 6b, R = OP(S)(OEt)2], were synthesized through the direct activation of various organic phosphorus compounds by N-heterocyclic ylide-like germylene 1.

η5–η1 ring slippage of [OsCp2] (Cp = η5-C5H5) and [Ru(η5-ind)2] (ind = indenyl) resulting from reaction with the ruthenium(VI) nitride [Ru(LOEt)(N)Cl2] (1; LOEt– = [CoCp{P(O)(OEt)2}3]−) is reported. The treatment of [OsCp2] or [Ru(η5-ind)2] with 1 resulted in η5-η1 ring slippage of the cycloolefin ligands and formation of the trinuclear nitrido complexes [Cp(η1-C5H5)Os(NRuLOEtCl2)2] (2) or [(η5-ind)(η1-ind)Ru(NRuLOEtCl2)2] (3).

In this paper, the trans influence of boryl ligands, together with that of other ligands commonly believed to have a strong trans influence, has been investigated theoretically via density functional theory (DFT) calculations on a series of square-planar platinum(II) complexes of the form trans-[PtL(Cl) (PMe3)(2)].