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The metastable purple [(Py5Me2)RuIII(N3)]2+ ion reacts with PPh3 at room temperature to form the phosphinimine complex [(Py5Me2)RuII(N(H)PPh3)]2+ and free [H2NPPh3]+ in a combined 23% conversion. Mechanistic studies suggest that this is the first metallo-Staudinger reaction of a late transition metal that bypasses the nitrido mechanism and instead utilizes a Ru-N[double bond, length as m-dash]N[double bond, length as m-dash]N-PPh3 phosphazide intermediate.

The location of the unpaired electron in the new mixed-valent (W2)(IV,V) trication [W2O(dpa)4](3+) presents a challenge for DFT methods. EPR spectroscopy confirms the unpaired electron to be in the W(V)-oxo unit, in agreement with the predictions of hybrid functionals B3LYP and TPSSh, but contrary to the predictions of non-hybrid functionals.

A new mixed-valent Rh(2)(II,III) dimer, [Rh(2)(espn)(2)Cl] (espn(2-) = α,α,α',α'-tetramethyl-1,3-benzenedipropanamidate), is reported. This compound readily dissociates Cl(-) at low concentrations in solution to form the active [Rh(2)(espn)(2)](+) catalyst, which performs intramolecular C-H amination with TONs > 1400. This work expands the scope of Rh(2)(II,III) dimers to nitrenoid chemistry.

Addition of CrCl(2) to the dinuclear synthon MoW(dpa)(4) yields a regioselectively formed heterotrimetallic Mo[quadruple bond]W...Cr chain; computational studies suggest that the polarization of the Mo[quadruple bond]W quadruple bond partially accounts for this unexpected selectivity.