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

Abstract

The 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 the air-stable trinuclear complexes in which the bis-phosphanido ligands (PPhPPh-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 the carbonyl compounds insertion 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).