Reactions of Manganese and Rhenium Vinylidene Complexes with Hydrophosphoryl Compounds
journal contribution
posted on 2016-11-28, 20:22 authored 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. UstynyukWe studied the reactions
of manganese and rhenium phenylvinylidenes
Cp(CO)2MCC(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]CC(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]CC(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)CC}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.
