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Reactions of Manganese and Rhenium Vinylidene Complexes with Hydrophosphoryl Compounds

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posted on 28.11.2016, 20:22 by Kamil I. Utegenov, Vasilii V. Krivykh, Andrei M. Mazhuga, Oleg S. Chudin, Aleksander F. Smol’yakov, Fedor M. Dolgushin, Evgenii I. Goryunov, Nikolai A. Ustynyuk
We studied the reactions of manganese and rhenium phenylvinylidenes Cp­(CO)2MCC­(H)­Ph (Mn1 M = Mn; Re1 M = Re) with HP­(O)­R2 (R = C6F5, Ph, and OEt) and HP­(S)­Ph2, which resulted in the selective formation of η2-E-phosphorylalkene complexes Cp­(CO)2M­{η2-E-H­[R2(O)­P]­CC­(H)­Ph} (Mn2, Re2 R = C6F5; Mn3, Re3 R = Ph; and Mn6, Re6 R = OEt) and Cp­(CO)2M­{η2-E-H­[Ph2(S)­P]­CC­(H)­Ph} (Mn5, Re5). The DFT/B3LYP­(6-31G*) analysis showed the model reactions of Mn1 with HP­(O)­Me2 and HP­(O) (OMe)2 to proceed via the initial transition state Cp­(CO)2{Ph­(H)­CC}­Mn···HO–PR2 (TS1) where the minor PA form HO–PR2 is hydrogen-bonded to the metal, followed by stereoselective (trans- to the phenyl group) addition of the PA phosphorus atom to the Cα-vinylidene atom, which defines both the rate of the process and the anti-Markovnikov structure of the reaction product. The reactions can proceed at a relatively low content of the reactive PA form.