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.

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.