1430654-22-0Relevant articles and documents
Electron-rich N-heterocyclic silylene (NHSi)-iron complexes: Synthesis, structures, and catalytic ability of an isolable hydridosilylene-iron complex
Blom, Burgert,Enthaler, Stephan,Inoue, Shigeyoshi,Irran, Elisabeth,Driess, Matthias
, p. 6703 - 6713 (2013/06/26)
The first electron-rich N-heterocyclic silylene (NHSi)-iron(0) complexes are reported. The synthesis of the starting complex is accomplished by reaction of the electron-rich Fe0 precursor [(dmpe)2Fe(PMe 3)] 1 (dmpe =1,2-bis(dimethylphosphino)ethane) with the N-heterocyclic chlorosilylene LSiCl (L = PhC(NtBu)2) 2 to give, via Me3P elimination, the corresponding iron complex [(dmpe)2Fe(←:Si(Cl)L)] 3. Reaction of in situ generated 3 with MeLi afforded [(dmpe)2Fe(←:Si(Me)L)] 4 under salt metathesis reaction, while its reaction with Li[BHEt3] yielded [(dmpe) 2Fe(←:Si(H)L)] 5, a rare example of an isolable SiII hydride complex and the first such example for iron. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analyses. DFT calculations further characterizing the bonding situation between the SiII and Fe0 centers were also carried out, whereby multiple bonding character is detected in all cases (Wiberg Bond Index >1). For the first time, the catalytic activity of a SiII hydride complex was investigated. Complex 5 was used as a precatalyst for the hydrosilylation of a variety of ketones in the presence of (EtO)3SiH as a hydridosilane source. In most cases excellent conversions to the corresponding alcohols were obtained after workup. The reaction pathway presumably involves a ketone-assisted 1,2-hydride transfer from the SiII to Fe0 center, as a key elementary step, resulting in a betaine-like silyliumylidene intermediate. The appearance of the latter intermediate is supported by DFT calculations, and a mechanistic proposal for the catalytic process is presented.
