Fac-to-mer isomerization triggers hydride transfer from Mn(I) complex fac-[(dppm)Mn(CO)3H]

Elena S. Osipova; Ekaterina S. Gulyaeva; Nikolay V. Kireev; Sergey A. Kovalenko; Christian Bijani; Yves Canac; Dmitry A. Valyaev; Oleg A. Filippov; Natalia V. Belkova; Elena S. Shubina

doi:10.1039/D2CC00999D

Fac-to-mer isomerization triggers hydride transfer from Mn(i) complex fac-[(dppm)Mn(CO)₃H]†

Elena S. Osipova,‡^a Ekaterina S. Gulyaeva,‡^ab Nikolay V. Kireev,^a Sergey A. Kovalenko,^a Christian Bijani,^b Yves Canac,

^b Dmitry A. Valyaev,

*^b Oleg A. Filippov,

*^a Natalia V. Belkova

^a and Elena S. Shubina

*^a

Author affiliations

* Corresponding authors

^a A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28 Vavilov str., GSP-1, B-334, Moscow, Russia
E-mail: h-bond@ineos.ac.ru, shu@ineos.ac.ru

^b LCC-CNRS, Université de Toulouse, CNRS, 205 route de Narbonne 31077 Toulouse, France
E-mail: dmitry.valyaev@lcc-toulouse.fr

Abstract

Low-temperature IR and NMR studies combined with DFT calculations revealed the mechanistic complexity of apparently simple reactions between Mn(I) complex fac-[(dppm)Mn(CO)₃H] and Lewis acids (LA = Ph₃C⁺, B(C₆F₅)₃) involving the formation of so-far elusive meridional hydride species mer-[(dppm)Mn(CO)₃H⋯LA] and unusual dearomatization of the Ph₃C⁺ cation upon hydride transfer.

Chemical Communications

Fac-to-mer isomerization triggers hydride transfer from Mn(i) complex fac-[(dppm)Mn(CO)₃H]†

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Fac-to-mer isomerization triggers hydride transfer from Mn(I) complex fac-[(dppm)Mn(CO)₃H]

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