Iron(0) pentacarbonyl complexes of gold(I), [Mes PAu-Fe(CO) ][SbF ] (1) and [(IPr*)Au-Fe(CO) ][SbF ] (2) (Mes=2,4,6-trimethylphenyl; IPr*=1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) have been synthesized using Mes PAuCl and (IPr*)AuCl as the gold(I) precursor, AgSbF halide ion abstractor, and the Lewis base Fe(CO) . The Au-Fe bond lengths of these metal-only Lewis pair complexes are significantly shorter than the sum of the experimentally derived covalent radii of Au and Fe. The v̄(CO) bands of the molecules show a notable blueshift relative to those observed for free Fe(CO) , indicating a substantial reduction in Fe→CO backbonding upon its coordination to gold(I) with either Mes P or IPr* supporting ligands (L). The analysis of the electronic structure with quantum chemical method suggests that the Au-Fe bond consists mainly of [LAu] ←Fe(CO) σ-donation and weaker [LAu] →Fe(CO) π-backdonation. The donor strength of Fe(CO) is similar to that of CO.
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