Slow magnetic relaxation in cobalt N-heterocyclic carbene complexes.

The combined experimental and theoretical investigation of the magnetic properties of the cobalt(ii) NHC complexes (NHC = N-heterocyclic carbene); [Co(CH2SiMe3)2(IPr)] (1), [CoCl2(IMes)2] (2) and [Co(CH3)2(IMes)2] (3) revealed a large easy plane anisotropy for 1 (D = +73.7 cm-1) and a moderate easy axis anisotropy for 2 (D = -7.7 cm-1) due to significant out-of-state spin-orbit coupling. Dynamic magnetic measurements revealed slow relaxation of the magnetization for 1 (Ueff = 22.5 K, τ0 = 3 × 10-7 s, 1000 Oe) and for 2 (Ueff = 20.2 K, τ0 = 1.73 × 10-8 s, 1500 Oe). The molecular origin of the slow relaxation phenomena was further supported by the retention of AC signal in 10% solutions in 2-MeTHF which reveals a second zero field AC signal in 1 at higher frequencies. Compound 3 was found to be an S = 1/2 system.

Homoleptic transition metal complexes of the 7-azaindolide ligand featuring κ(1)-N1 coordination.

Homoleptic complexes of the anion of 7-azaindole (AzaIn) were synthesized and characterized for a series of 3d transition metals. For Mn(II), Fe(II), and Co(II), complexes of formula Na2[M(AzaIn)4]·2L (L = tetrahydrofuran (THF), 2-MeTHF, toluene, or benzene) were isolated by treatment of the corresponding metal chloride salts with 7-azaindole in the presence of sodium hexamethyldisilazide. The complexes adopt tetrahedral geometries with exclusive coordination to the transition metal ion through the pyrrolic N1 nitrogen atoms of the AzaIn ligands. Solid-state structures of the complexes demonstrate that the sodium cations remain tightly associated with the coordination entities through interaction with both the pyrrolic and pyridine nitrogen atoms of the azaindolide ligands. For Fe(II), replacement of the sodium cations by other alkali metal ions (Li or K) generates new complexes that demonstrate similar coordination geometries to the sodium salts. As a means of comparison, the Fe(II) complex of 4-azaindolide was also investigated. Na2[Fe(4-AzaIn)4]·2L adopts a similar solution structure to the 7-azaindolide complexes as judged by NMR spectroscopy and cyclic voltammetry. Density functional theory calculations were performed to investigate the bonding in the 7-azaindolide complexes. Results demonstrate that 7-azaindolide-κ(1)-N1 is a nearly pure sigma donor ligand that features a high degree of ionic character in its bonding to mid 3d transition metal ions.

A combined magnetic circular dichroism and density functional theory approach for the elucidation of electronic structure and bonding in three- and four-coordinate iron(II)-N-heterocyclic carbene complexes.

The combination of iron salts and N-heterocyclic carbene (NHC) ligands is a highly effective combination in catalysis, with observed catalytic activities being highly dependent on the nature of the NHC ligand. Detailed spectroscopic and electronic structure studies have been performed on both three- and four-coordinate iron(II)-NHC complexes using a combined magnetic circular dichroism (MCD) and density functional theory (DFT) approach that provide detailed insight into the relative ligation properties of NHCs compared to traditional phosphine and amine ligands as well as the effects of NHC backbone structural variations on iron(II)-NHC bonding. Near-infrared MCD studies indicate that 10Dq(Td) for (NHC)2FeCl2 complexes is intermediate between those for comparable amine and phosphine complexes, demonstrating that such iron(II)-NHC and iron(II)-phosphine complexes are not simply analogues of one another. Theoretical studies including charge decomposition analysis indicate that the NHC ligands are slightly stronger donor ligands than phosphines but also result in significant weakening of the Fe-Cl bonds compared to phosphine and amine ligands. The net result is significant differences in the d orbital energies in four-coordinate (NHC)2FeCl2 complexes relative to the comparable phosphine complexes, where such electronic structure differences are likely a significant contributing factor to the differing catalytic performances observed with these ligands. Furthermore, Mössbauer, MCD and DFT studies of the effects of NHC backbone structure variations (i.e. saturated, unsaturated, chlorinated) on iron-NHC bonding and electronic structure in both three- and four-coordinate iron(II)-NHC complexes indicate only small differences as a function of backbone structure, that are likely amplified at lower oxidation states of iron due to the resulting decrease in the energy separation between the occupied iron d orbitals and the unoccupied NHC π* orbitals.

Dinuclear and heptanuclear complexes of copper(II) with 7-azaindole ligand: synthesis, characterization, magnetic properties, and biological activity.

Three new complexes of Cu(II) with 7-azaindole have been synthesized and characterized, a dicopper compound, [Cu(C7H5N2)2(H2O)]2·2CH3CN, 1, and two heptacopper compounds [Cu7(C7H5N2)6(µ3-OH)6(µ2-H2O)2(µ2-CH3OH)4](CH3COO)2·2C7H8·6CH3OH, 2, and [Cu7(C7H5N2)5(CH3COO)(µ3-OH)6(µ2-H2O)4(µ2-CH3OH)2](CH3COO)2, 4. The structure of 2 is monoclinic and it crystallizes in the P21/c space group: a=13.475(4)Å; b=12.945(4)Å; c=23.392(7)Å; ß=91.232(6)°. It contains a unique Cu7O12 core in which a central Cu(II) is situated at an inversion center and is bonded to 6 other Cu(II) ions via bridging oxygen atoms from OH(-), H2O, and CH3OH groups. Anionic 7-azaindole ligands bridge between adjacent outer Cu(II) ions and all Cu(II) ions have distorted octahedral coordination geometries. Variable temperature magnetic susceptibility measurements revealed the presence of antiferromagnetic exchange interactions between Cu(II) ions which leads to an S=5/2 ground state at 1.8K. Cytotoxicity and cell proliferation activities of the Cu compounds using human tongue squamous cell carcinoma and normal cells revealed that the compounds stimulated proliferation in both types of cells.