Utilization of Phosphinoamide Ligands in Homobimetallic Fe and Mn Complexes: The Effect of Disparate Coordination Environments on Metal–Metal Interactions and Magnetic and Redox Properties

A series of homobimetallic phosphinoamide-bridged diiron and dimanganese complexes in which the two metals maintain different coordination environments have been synthesized. Systematic variation of the steric and electronic properties of the phosphinoamide phosphorus and nitrogen substituents leads to structurally different complexes. Reaction of [^<i>i</i>PrNKPPh₂] (<b>1</b>) with MCl₂ (M = Mn, Fe) affords the phosphinoamide-bridged bimetallic complexes [Mn­(^<i>i</i>PrNPPh₂)₃Mn­(^<i>i</i>PrNPPh₂)] (<b>3</b>) and [Fe­(^<i>i</i>PrNPPh₂)₃Fe­(^<i>i</i>PrNPPh₂)] (<b>4</b>). Complexes <b>3</b> and <b>4</b> are iso-structural, with one metal center preferentially binding to the three amide ligands in a trigonal planar arrangement while the second metal center is ligated by three phosphine donors. A fourth phosphinoamide ligand caps the tetrahedral coordination sphere of the phosphine-ligated metal center. Mössbauer spectroscopy of complex <b>4</b> suggests that the metals in these complexes are best described as Fe^II centers. In contrast, treatment of MnCl₂ or FeI₂ with [MesNKP^<i>i</i>Pr₂] (<b>2</b>) leads to the formation of the halide-bridged species [(THF)­Mn­(μ-Cl)­(MesNP^<i>i</i>Pr₂)₂Mn­(MesNP^<i>i</i>Pr₂)] (<b>5</b>) and [(THF)­Fe­(μ-I)­(MesNP^<i>i</i>Pr₂)₂FeI (<b>7</b>), respectively. Utilization of FeCl₂ in place of FeI₂, however, leads exclusively to the C₃-symmetric complex [Fe­(MesNP^<i>i</i>Pr₂)₃FeCl] (<b>6</b>), structurally similar to <b>4</b> but with a halide bound to the phosphine-ligated Fe center. The Mössbauer spectrum of <b>6</b> is also consistent with high spin Fe^II centers. Thus, in the case of the [^<i>i</i>PrNPPh₂]⁻ and [MesNP^<i>i</i>Pr₂]⁻ ligands, zwitterionic complexes with the two metals in disparate coordination environments are preferentially formed. In the case of the more electron-rich ligand [^<i>i</i>PrNP^<i>i</i>Pr₂]⁻, complexes with a 2:1 mixed donor ligand arrangement, in which one of the ligand arms has reversed orientation relative to the previous examples, are formed exclusively when [^<i>i</i>PrNLiP^<i>i</i>Pr₂] (generated in situ) is treated with MCl₂ (M = Mn, Fe): (THF)₃LiCl­[Mn­(N^<i>i</i>PrP^<i>i</i>Pr₂)₂(P^<i>i</i>Pr₂N^<i>i</i>Pr)­MnCl] (<b>8</b>) and [Fe­(N^<i>i</i>PrP^<i>i</i>Pr₂)₂(P^<i>i</i>Pr₂N^<i>i</i>Pr)­FeCl] (<b>9</b>). Bimetallic complexes <b>3</b>–<b>9</b> have been structurally characterized using X-ray crystallography, revealing Fe–Fe interatomic distances indicative of metal–metal bonding in complexes <b>6</b> and <b>9</b> (and perhaps <b>4</b>, to a lesser extent). All of the complexes appear to adopt high spin electron configurations, and magnetic measurements indicate significant antiferromagnetic interactions in Mn₂ complexes <b>5</b> and <b>8</b> and no discernible magnetic superexchange in Fe₂ complex <b>4</b>. The redox behavior of complexes <b>3</b>–<b>9</b> has also been investigated using cyclic voltammetry, and theoretical investigations (DFT) were performed to gain insight into the metal–metal interactions in these unique asymmetric complexes