Results
Title

Cationic Tetrylene‐Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open‐Shell Iron(−I) Ferrato‐Tetrylenes**.

Authors

Keil, Philip M.; Soyemi, Ademola; Weisser, Kilian; Szilvási, Tibor; Limberg, Christian; Hadlington, Terrance J.

Abstract

The open‐shell cationic stannylene‐iron(0) complex 4 (4=[PhiPDippSn⋅Fe⋅IPr] ; PhiPDipp={[Ph2PCH2Si(iPr)2](Dipp)N}; Dipp=2,6‐iPr2C6H3; IPr=[(Dipp)NC(H)]2C:) cooperatively and reversibly cleaves dihydrogen at the Sn−Fe interface under mild conditions (1.5 bar, 298 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 PhiPDipp 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.

Subjects

ELECTRON spin; OXIDATIVE addition; ELECTRON paramagnetic resonance spectroscopy; ELECTRON density; IRON; TIN

Publication

Angewandte Chemie, 2023, Vol 135, Issue 19, p1

ISSN

0044-8249

Publication type

Academic Journal

DOI

10.1002/ange.202218141