Structural and two-dimensional phosphorus-31 nuclear magnetic resonance studies of derivatives from (RP)₅(R = Et or Ph) and activated triosmium clusters [Os₃(CO)₁₀X₂](X =µ-H or NCMe)

Abstract

The reaction of the cyclophosphane (EtP)5 with the activated triosmium cluster [Os3(µ-H)2(CO)10] at 80 °C gave [Os3(µ-H)(CO)8(µ-η3-P5Et5H)]1 and [Os3(CO)10{1,3-(PEt)5}]2. The compound (PhP)5 reacted with [Os3(µ-H)2(CO)10] at room temperature to give [Os3(µ-H)(CO)8(µ-η3-P5Ph5H)]3. Treatment of (EtP)5 with [Os3(CO)10(NCMe)2] at room temperature afforded [Os3(CO)10{1,2-(PEt)5}]4, while the reaction at 80 °C yielded only 2. All the reaction products have been characterized by elemental analysis and IR, 1H and 31P NMR spectroscopy. The solid-state structures of compounds 1, 2 and 4 established by single-crystal X-ray diffraction showed that the phosphorus ring in 1 has undergone one P–P bond cleavage while those in 2 and 4 are intact. The solution structure of 3 has been fully characterized by two-dimensional 31P NMR spectroscopy.