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

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 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)(7)O-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 P-31 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).

Automated summary

In the presence of [Mo(CO)(4)(cod)], the reaction of cyclopentaphosphine cyclo-(P5Ph5) with ketones (acetone and cyclooctanone) led to the formation of air-stable trinuclear complexes. These complexes contain bis-phosphanido ligands (PPh-PPh-PPh-PPh-CMe2O-PPh)(2-) and (PPh-PPh-PPh-PPh-C(CH2)(7)O-PPh)(2-) bridging a Mo(CO)(3)-Mo(CO)(3) unit. This reaction expands the substrate scope of 1 with transition metal carbonyl complexes and represents the first examples of carbonyl compound insertion into the P-P bond of cyclic oligophosphorus compounds. The structures of complexes 2 and 3 have been characterized by P-31 NMR and single crystal X-ray diffraction. Furthermore, the thermal properties of the complexes have been studied using differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC).