Protonation of Zwitterionic Manganese and Rhenium Phosphoniostyryl Complexes (η 5 ‐C 5 H 5 )(CO) 2 M – –C( + PR 3 )=C(H)Ph: Experimental and DFT Study

Vasily Krivykh (1) , Dmitry A. Valyaev (1) , Kamil Utegenov (1) , Andrei Mazhuga (1) , Elena Taits (1) , Oleg Semeikin (1) , Pavel Petrovskii (1) , Ivan Godovikov (1) , Ivan Glukhov (1) , Nikolai Ustynyuk (1)

1 INEOS - A. N. Nesmeyanov Institute of Organoelement Compounds

Protonation of Mn and Re Z-σ-phosphoniostyryl complexes 3–7 with HBF4·OEt2 leads to the E-η2-phosphonioalkene derivatives 8–12 rather than the phosphoniocarbene complexes 13. According to DFT calculations, protonation of Mn complex 5 proceeds at the metal atom followed by fast conversion of the resulting cis-hydride 14 into the agostic intermediate 15 and the final product 10. Quantitative formation of the cis-hydride intermediates 16 and 17 was evidenced by low-temperature protonation of the rhenium Z-σ-phosphoniostyryl complexes 6 and 7 with triflic acid.

Mots clés: Vinylidene complexes; Manganese; Rhenium; Protonation; Zwitterions; X-ray diffraction; Density functional calculations

Domaines: Chimie de coordination

Vasily Krivykh, Dmitry A. Valyaev, Kamil Utegenov, Andrei Mazhuga, Elena Taits, et al.. Protonation of Zwitterionic Manganese and Rhenium Phosphoniostyryl Complexes (η 5 ‐C 5 H 5 )(CO) 2 M – –C( + PR 3 )=C(H)Ph: Experimental and DFT Study. European Journal of Inorganic Chemistry, 2011, 2011 (2), pp.201-211. ⟨10.1002/ejic.201000868⟩. ⟨hal-03739903⟩