Inorg. Chem.

Reaction Mechanisms on [3 + 2] Cycloaddition of Azides with Metal Carbyne Complexes: Significant Effects of Aromaticity, Substituent, and Metal Center

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.

Formation of Iridium(III) Complexes via Selective Activation of the C–H and N–H Bonds of a Dipyridylpyrrole Ligand

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.

Reactivity of Germylene toward Phosphorus-Containing Compounds: Nucleophilic Addition and Tautomerism

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.

Facile η5–η1 Ring Slippage of the Cycloolefin Ligands in Osmocene and Bis(η5-indenyl)ruthenium(II)

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).

Trans Influence of Boryl Ligands and Comparison with C, Si, and Sn Ligands

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)].