Abstract
A new synthetic access to oligodentate phosphine ligands with phospholane end groups, starting from lithium phospholanide, is established. Based on this building block, the tridentate ligand prPP(Ph)P‐pln was synthesized and used for the synthesis of [MoX3{prPP(Ph)P‐pln}] (X = Cl, Br, I) precursors. Sodium amalgam reduction in the presence of N2 and either mono‐ or bidentate ligands leads to several molybdenum(0) mono‐ and bis(dinitrogen) complexes, respectively. With the diphosphine dppm a mixture of facial and meridional isomers of [Mo(N2){prPP(Ph)P‐pln}(dppm)] is formed. Using the monophosphines PMePh2 and PMe2Ph mer‐[Mo(N2){prPP(Ph)P‐pln}(PMe2Ph)2] and trans‐[Mo(N2)2{prPP(Ph)P‐pln}(PMePh2)] could be obtained. The spectroscopic properties and reactivity of the latter towards protonation was investigated, and a hydrazido complex could be obtained and characterized.
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