Cationic Tetrylene-Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open-Shell Iron(-I) Ferrato-Tetrylenes.
Angew Chem Int Ed Engl
; 62(19): e202218141, 2023 May 02.
Article
em En
| MEDLINE
| ID: mdl-36757051
ABSTRACT
The open-shell cationic stannylene-iron(0) complex 4 (4=[PhiP DippSnâ
Feâ
IPr]+ ; PhiP Dipp={[Ph2 PCH2 Si(i Pr)2 ](Dipp)N}; Dipp=2,6-i Pr2 C6 H3 ; IPr=[(Dipp)NC(H)]2 C) cooperatively and reversibly cleaves dihydrogen at the Sn-Fe interface under mild conditions (1.5â
bar, 298â
K), in forming bridging hydrido-complex 6. The One-electron oreduction of the related GeII -Fe0 complex 3 leads to oxidative addition of one C-P linkage of the PhiP Dipp ligand in an intermediary Fe-I complex, leading to FeI phosphide species 7. One-electron reduction reaction of 4 gives access to the iron(-I) ferrato-stannylene, 8, giving evidence for the transient formation of such a species in the reduction of 3. The covalently bound tin(II)-iron(-I) compound 8 has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe-I in this unique d9 -iron complex.
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1
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
Alemanha