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-P 5Et5H)] 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-P 5Ph5H)] 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.