Synthesis and characterization of heterometallic complexes involving coinage metals and isoelectronic Fe(CO)₅, [Mn(CO)₅]⁻and [Fe(CO)₄CN]⁻ligands

Abstract

Metallo adducts involving Cu(i), Ag(i) and Au(i) Lewis acids and iron and manganese centered organometallic Lewis bases have been investigated using phosphine and N-heterocyclic carbene supporting ligands.

Structural Characterization and Bonding Analysis of [Hg{Fe(CO)5}2]2+ [SbF6]−2

“…This is different from classical TM complexes, which are best described with the Dewar–Chatt–Duncanson model in terms of σ donation and the usually stronger π back-donation . It is also different from nonclassical carbonyl complexes where the metal atom is a σ acceptor …”

“…The synthesis of the originally desired [Fe­(CO) 5 ] + was achieved only in 2022 by a silver-free route . Related heterobimetallic Ag–Fe and Au–Fe complexes containing the Fe­(CO) 5 moiety were later synthesized by the Dias group. − In this context also, a combined experimental and theoretical study by Dias et al . about the complete series of group 11 complexes [M­{Fe­(CO) 5 } 2 ] + (M = Cu, Ag, Au) is especially noteworthy …”

Copper(i) and silver(i) chemistry of vinyltrifluoroborate supported by a bis(pyrazolyl)methane ligand

“…Deuterated solvents were purchased from Acros Organics and Cambridge Isotope Laboratories, respectively. K(CH 2 vCHBF 3 ), 13 CH 2 (3,5-(CH 3 ) 2 Pz) 2 33 and (SIPr)CuNO 3 34 were prepared according to the procedures reported in the literature.…”

Coordination versus Insertion: On the Interaction of 5 d‐Transition Metal Carbonyl Clusters with Silver(I)

“…Applied to coinage metal(I) complexes of the TMCs, the MOLP concept and EDA-NOCV analyses suggest that the most important interaction in both series of the complex cations [M{Fe(CO) 5 } 2 ] + (M=Cu, Ag, Au) and [Ag({M'(CO) 6 } 2 ] + (M' = Mo, W) is the donation of electron density from the HOMO orbitals of the TMCs into the vacant s-and p-orbitals of the silver(I) cation. [7,8,22] Moreover, we recently prepared the [Ag{M 3 (CO) 12 } 2 ] + (M=Ru, Os) complex salts as the product of the reaction of a silver(I) WCA salt with the respective trimetal dodecacarbonyls. The reaction was originally directed towards the preparation of clustered homoleptic transition metal carbonyl cations.…”