Protonation of Zwitterionic Manganese and Rhenium Phosphoniostyryl Complexes (η5-C5H5)(CO)2M––C(+PR3)=C(H)Ph: Experimental and DFT Study (pages 201–211)
Vasily V. Krivykh, Dmitry A. Valyaev, Kamil I. Utegenov, Andrei M. Mazhuga, Elena S. Taits, Oleg V. Semeikin, Pavel V. Petrovskii, Ivan A. Godovikov, Ivan V. Glukhov and Nikolai A. Ustynyuk
Version of Record online: 12 NOV 2010 | DOI: 10.1002/ejic.201000868
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.