Molybdenum‐Mediated Insertion of Ketones into the P−P bond of cyclo‐(P5Ph5) and Formation of Trinuclear Molybdenum Complexes

Abstract

AbstractThe reaction of cyclopentaphosphine cyclo‐(P5Ph5) (1) with ketones (acetone and cyclooctanone) in the presence of [Mo(CO)4(cod)] (cod=cycloocta‐1,5‐diene) led to air‐stable trinuclear complexes in which the bis‐phosphanido ligands (PPh−PPh−PPh−PPh−CMe2O−PPh)2− (complex 2) and (PPh−PPh−PPh−PPh−C(CH2)7O−PPh)2− (complex 3) bridge a Mo(CO)3−Mo(CO)3 unit. This extends the reaction of 1 with transition metal carbonyl complexes to further substrates and represents the first examples of insertion of carbonyl compounds into the P−P bond of cyclic oligophosphorus compounds. Complexes 2 and 3 have been characterized by 31P NMR spectroscopy and single crystal X‐ray diffraction. Furthermore, the thermal properties of the obtained complexes have been studied by differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC).