The preparation and characterization of two NiII complexes are described, a terminal NiII-OH complex with the tripodal ligand tris[(N)-tertbutylureaylato)-N-ethyl)]aminato ([H3buea]3-) and a terminal Ni II-OH2 complex with the tripodal ligand N,N',N″-[2,2',2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST]3-). For both complexes, the source of the -OH and -OH2 ligand is water. The salts K2[NiIIH3buea(OH)] and NMe4[NiIIMST(OH2)] were characterized using perpendicular-mode X-band electronic paramagnetic resonance, Fourier transform infrared, UV-visible spectroscopies, and its electrochemical properties were evaluated using cyclic voltammetry. The solid state structures of these complexes determined by X-ray diffraction methods reveal that they adopt a distorted trigonal bipyramidal geometry, an unusual structure for 5-coordinate NiII complexes. Moreover, the NiII-OH and NiII-OH2 units form intramolecular hydrogen bonding networks with the [H3buea]3- and [MST]3- ligands. The oxidation chemistry of these complexes was explored by treating the high-spin NiII compounds with one-electron oxidants. Species were formed with S = 1/2 spin ground states that are consistent with formation of monomeric NiIII species. While the formation of NiIII-OH complexes cannot be ruled out, the lack of observable O-H vibrations from the putative Ni-OH units suggest the possibility that other high valent Ni species are formed.

A series of bimetallic complexes prepared with the ligands N,N,N',N'-tetramethylethane-1,2-diamine (TMEDA) and N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST]3-) is described. Four diiron compounds of the formulation (TMEDA)FeII(X)-(μ-OH)-FeIIIMST were prepared, in which the X- ligands are the anions OTf-, Br-, SCN-, or N3-. Additionally, two heterobimetallic compounds of the formulation (TMEDA)MII(OTf)-(μ-OH)-FeIIIMST (MII = CoII or NiII) were synthesized. All these compounds have similar spectroscopic and structural properties. The diiron compounds exhibit perpendicular-mode electron paramagnetic resonance spectra consistent with S = 1/2 spin ground states, which is expected for high-spin FeII and FeIII centres that are antiferromagnetically coupled. The heterobimetallic (TMEDA)NiII(OTf)-(μ-OH)-FeIIIMST complex had a spin state of S = 3/2 that also resulted from antiferromagnetic coupling between the high-spin NiII and FeIII centres. The modularity of this system is further demonstrated by the substitution of the TMEDA ligand with ethylenediamine (en); for this species two equivalents of en coordinate to the FeII centre to form [(en)2FeII-(μ-OH)-FeIIIMST]OTf. These results demonstrate that a modular bimetallic system has been developed in which the key components can be modified.

Heterobimetallic cores are important units within the active sites of metalloproteins but are often difficult to duplicate in synthetic systems. We have developed a synthetic approach for the preparation of a complex with a Mn(II)-(μ-OH)-Fe(III) core, in which the metal centers have different coordination environments. Structural and physical data support the assignment of this complex as a heterobimetallic system. A comparison with analogous homobimetallic complexes, Mn(II)-(μ-OH)-Mn(III) and Fe(II)-(μ-OH)-Fe(III) cores, further supports this assignment.

Bimetallic complexes are important sites in metalloproteins but are often difficult to prepare synthetically. We have previously introduced an approach to form discrete bimetallic complexes with MII-(μ-OH)-FeIII (MII = Mn, Fe) cores using the tripodal ligand N,N',N″-[2,2',2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST]3-). This series is extended to include the rest of the late 3d transition metal ions (MII = Co, Ni, Cu, Zn). All of the bimetallic complexes have similar spectroscopic and structural properties that reflect little change despite varying the MII centers. Magnetic studies performed on the complexes in solution using electron paramagnetic resonance spectroscopy showed that the observed spin states varied incrementally from S = 0 through S = 5/2; these results are consistent with antiferromagnetic coupling between the high-spin MII and FeIII centers. However, the difference in the MII ion occupancy yielded only slight changes in the magnetic exchange coupling strength, and all complexes had J values ranging from +26(4) to +35(3) cm-1.