P–C, P–N, and M–N Bond Formation Processes in Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Diazoalkanes and Organic Azides to Build Three- to Five-Membered Phosphametallacycles

[Image: see text] Reactions of the heterometallic MoRe complex [MoReCp(μ-PR*)(CO)(6)] and its MoMn analogue with some small molecules having N–N multiple bonds, such as diazoalkanes and organic azides, were investigated (R* = 2,4,6-C(6)H(2)(t)Bu(3)). Reactions with excess ethyl diazoacetate proceeded slowly and with concomitant denitrogenation to give complexes [MoMCp(μ-η(2)(P,C):κ(2)(P,O)-PR*CHCO(2)Et)(CO)(5)], which display a bridging phosphaalkene ligand in a novel μ-η(2):κ(2) coordination mode, while reactions with other diazoalkanes resulted only in the decomposition of the organic reagent. The MoRe complex reacted with benzyl- or p-tolyl azide at room temperature to give the green complexes [MoReCp(μ-η(2)(P,N):κ(P,N′)(2)-PR*N(3)R)(CO)(6)] [R = Bn, p-tol], which display bridging phosphatriazadiene ligands in a novel 6-electron donor coordination mode as a result of a formal [2 + 1] cycloaddition of the terminal N atom of the azide to the Mo–P double bond of the parent complex, followed by coordination of the distal NR nitrogen to the rhenium center. Denitrogenation was only observed for the p-tolyl azide derivative, which upon heating at 333 K yielded [MoReCp{μ-κ(P):κ(N)-PR*N(p-tol)}(CO)(6)], a molecule displaying a bridging phosphaimine ligand in a rare κ(P):κ(N) coordination mode. Analogous reactions of the MoMn phosphinidene complex proceeded similarly at 273 K to give the phosphatriazadiene-bridged derivatives [MoMnCp(μ-η(2)(P,N):κ(2)(P,N′)-PR*N(3)R)(CO)(6)], but these were thermally unstable and degraded at room temperature to give the mononuclear triazenylphosphanyl complexes [Mn(2)(κ(P,N)-PR*NHNNR)(CO)(3)] as major products, along with small amounts of the phosphaimine-bridged complex [MoMnCp{μ-κ(P):κ(N)-PR*N(p-tol)}(CO)(6)] in the case of the p-tolyl azide derivative. The structure of the new complexes was analyzed in light of spectroscopic data and single-crystal diffraction studies on selected examples of each type of complex.