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

Abstract

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)PrNKPPh(2)] (1) with MCl(2) (M = Mn, Fe) affords the phosphinoamide-bridged bimetallic complexes [Mn((i)PrNPPh(2))(3)Mn((i)PrNPPh(2))] (3) and [Fe((i)PrNPPh(2))(3)Fe((i)PrNPPh(2))] (4). Complexes 3 and 4 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 4 suggests that the metals in these complexes are best described as Fe(II) centers. In contrast, treatment of MnCl(2) or FeI(2) with [MesNKP(i)Pr(2)] (2) leads to the formation of the halide-bridged species [(THF)Mn(μ-Cl)(MesNP(i)Pr(2))(2)Mn(MesNP(i)Pr(2))] (5) and [(THF)Fe(μ-I)(MesNP(i)Pr(2))(2)FeI (7), respectively. Utilization of FeCl(2) in place of FeI(2), however, leads exclusively to the C(3)-symmetric complex [Fe(MesNP(i)Pr(2))(3)FeCl] (6), structurally similar to 4 but with a halide bound to the phosphine-ligated Fe center. The Mössbauer spectrum of 6 is also consistent with high spin Fe(II) centers. Thus, in the case of the [(i)PrNPPh(2)](-) and [MesNP(i)Pr(2)](-) ligands, zwitterionic complexes with the two metals in disparate coordination environments are preferentially formed. In the case of the more electron-rich ligand [(i)PrNP(i)Pr(2)](-), 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)PrNLiP(i)Pr(2)] (generated in situ) is treated with MCl(2) (M = Mn, Fe): (THF)(3)LiCl[Mn(N(i)PrP(i)Pr(2))(2)(P(i)Pr(2)N(i)Pr)MnCl] (8) and [Fe(N(i)PrP(i)Pr(2))(2)(P(i)Pr(2)N(i)Pr)FeCl] (9). Bimetallic complexes 3-9 have been structurally characterized using X-ray crystallography, revealing Fe-Fe interatomic distances indicative of metal-metal bonding in complexes 6 and 9 (and perhaps 4, to a lesser extent). All of the complexes appear to adopt high spin electron configurations, and magnetic measurements indicate significant antiferromagnetic interactions in Mn(2) complexes 5 and 8 and no discernible magnetic superexchange in Fe(2) complex 4. The redox behavior of complexes 3-9 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.

Synthesis and Characterization of [M2(NCtBu2)5]− (M=Mn, Fe, Co): Metal Ketimide Complexes with Strong Metal–Metal Interactions

“…Interestingly, the terminal MnÀN bond length for 1 is 0.1 longer than that exhibited by the related Mn II ketimde, [Mn 3 (N = CtBu 2 ) 6 ], [5b] which does not possess a metal-metal bond (Mn1 À Mn2 2.8183 (8) ), suggesting the presence of a trans influence from the Mn-Mn interaction in 1 (see below).The most notable structural features for complexes 1-3 are the M À M distances (Mn 2.5965(7) , Fe 2.443(1) , Co 2.4097 (7) ). These M À M distances are amongst the shortest reported for late first-row transition-metal complexes with an M 2 4+ core, [6] and in the case of 2 and 3, are suggestive of an MÀ M bond. [2b] For comparison, the isostructural thiolates [M 2 (SR) 5 ] À feature longer MÀM distances, [7] ranging from 2.491(1) (M = Co, R = iPr) to 2.634(1) (M = Fe, R = iPr) and 2.607(3) (M = Ni, R = 2,4,6-iPr 3…”

“…The most notable structural features for complexes 1-3 are the M À M distances (Mn 2.5965 (7) , Fe 2.443(1) , Co 2.4097 (7) ). These M À M distances are amongst the shortest reported for late first-row transition-metal complexes with an M 2 4+ core, [6] and in the case of 2 and 3, are suggestive of an MÀ M bond. [2b] For comparison, the isostructural thiolates [M 2 (SR) 5 ] À feature longer MÀM distances, [7] ranging from 2.491(1) (M = Co, R = iPr) to 2.634(1) (M = Fe, R = iPr) and 2.607(3) (M = Ni, R = 2,4,6-iPr 3 C 6 H 2 ).…”

“…Each complex features two terminal ketimide ligands and three bridging ketimide ligands, resulting in the formation of two co-facial tetrahedra ( Figure 1). 6(1)8, Fe 72. 6(1)8, Fe 72.…”

“…[9] Both complexes are thought to feature direct FeÀFe bonds. Finally, the Co 2 4+ complex [Co 2 (DPhF) 3 - 6 ] has a Co···Co distance of 2.885(1) , [10] indicating that no direct Co À Co bond is present. We endeavored to probe the magnetic properties of complexes 1-3 to gain additional insight into the nature of the short metal-metal distances observed in the solid state.…”

Homo- and heteroleptic group 4 2-(diphenylphosphino)pyrrolide complexes: Synthesis, coordination chemistry and solution state dynamics

“…Unlike traditional tetragonal bimetallics, trigonal systems with weaker ligand fields should promote more favorable metal-metal bonding interactions. Systematic analysis of different metal pairs and ligand donor sets has allowed Lu and Thomas example, metal-metal bonding with the first row transition metals is typically best when metals and coordination environments are similar, and becomes weaker (ultimately leading to the inability to form d-and p-bonds) as the metals and/or their coordination environments become more disparate [47][48][49][50][51][52][53][54][55][56]. In the case of first row late transition metals paired with heavier second and third row early metals, multiple bonding is possible, although highly polarized [21].…”