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.