A Paramagnetic Nickel-Zinc Hydride Complex.

Reaction of a molecular zinc-hydride [{(ArNCMe)2CH}ZnH] (Ar = 2,6-di-isopropylphenyl) with 0.5 equiv. of [Ni(CO)Cp]2 led to the isolation of a nickel-zinc hydride complex containing a bridging 3-centre,2-electron Ni-H-Zn interaction. This species has been characterized in the solid-state by single crystal X-ray diffraction. DFT calculations are consistent with its formulation as a σ-complex derived from coordination of the zinc-hydride to a paramagnetic nickel(I) fragment. Continuous wave and pulse EPR experiments suggest that this species is not stable in solution and suggest that this species is labile in solution. Further experiments show that in the presence of catalytic quantities of nickel(I) precursors, zinc-hydride bonds can undergo either H/D-exchange with D2 or dehydrocoupling to form Zn-Zn bonds. In combination, the data support the activation and functionalisation of zinc-hydride bonds at nickel(I) centres.

X-ray absorption and emission spectroscopy of N2S2 Cu(II)/(III) complexes.

This study investigates the influence of ligand charge on transition energies in a series of CuN2S2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kß valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(II) complexes [CuII(HL1)] (HL12- = dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [CuII(HL2)] (HL22- = dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(III) complex [CuIII(L2)], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L23- ligand stabilizes the Cu(III) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(III) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.

Synthesis and redox activity of carbene-coordinated group 13 metal radicals.

Carbenes are known to stabilize main group element compounds with unusual electronic properties. Herein, we report the synthesis of carbene-stabilized group 13 metal radicals (cAAC)MX2(IPr) (M = Al, X = Br 3; M = Ga, X = Cl 4) and the corresponding cations [(cAAC)MX2(IPr)][B(C6F5)4] (M = Al, X = Br 5; M = Ga, X = Cl 6), which were characterized spectroscopically and by sc-XRD. Quantum chemical calculation gave insights into their electronic structures.

Combining Valence-to-Core X-ray Emission and Cu K-edge X-ray Absorption Spectroscopies to Experimentally Assess Oxidation State in Organometallic Cu(I)/(II)/(III) Complexes.

A series of organometallic copper complexes in formal oxidation states ranging from +1 to +3 have been characterized by a combination of Cu K-edge X-ray absorption (XAS) and Cu Kß valence-to-core X-ray emission spectroscopies (VtC XES). Each formal oxidation state exhibits distinctly different XAS and VtC XES transition energies due to the differences in the Cu Zeff, concomitant with changes in physical oxidation state from +1 to +2 to +3. Herein, we demonstrate the sensitivity of XAS and VtC XES to the physical oxidation states of a series of N-heterocyclic carbene (NHC) ligated organocopper complexes. We then extend these methods to the study of the [Cu(CF3)4]- ion. Complemented by computational methods, the observed spectral transitions are correlated with the electronic structure of the complexes and the Cu Zeff. These calculations demonstrate that a contraction of the Cu 1s orbitals to deeper binding energy upon oxidation of the Cu center manifests spectroscopically as a stepped increase in the energy of both XAS and Kß2,5 emission features with increasing formal oxidation state within the [Cun+(NHC2)]n+ series. The newly synthesized Cu(III) cation [CuIII(NHC4)]3+ exhibits spectroscopic features and an electronic structure remarkably similar to [Cu(CF3)4]-, supporting a physical oxidation state assignment of low-spin d8 Cu(III) for [Cu(CF3)4]-. Combining XAS and VtC XES further demonstrates the necessity of combining multiple spectroscopies when investigating the electronic structures of highly covalent copper complexes, providing a template for future investigations into both synthetic and biological metal centers.

Observation of Discrete Valence Tautomers in Crystalline Cyclopentadienyl Radicals.

Single crystal X-ray (sc XRD) analyses of three symmetrically substituted cyclopentadienyl radicals (1, 2, 5) containing sterically demanding aryl groups showed that they crystallize as discrete valence tautomers (Jahn-Teller distortion) in the solid state with the unpaired electron either located in the b1 orbital (type I, state 2B1), resulting in a localized radical with two adjacent double bonds, or the a2 orbital (type II, state 2A2), leading to an allyl-type radical. Their properties in solution were examined by EPR spectroscopy as well as cyclovoltammetry and UV/vis spectroscopy including two additional cyclopentadienyl radicals (1-5). The electronic nature of 1-5 was further investigated by quantum chemical calculations.

Redox Activity of Noninnocent 2,2'-Bipyridine in Zinc Complexes: An Experimental and Theoretical Study.

We report on a systematical reactivity study of ß-diketiminate zinc complexes with redox-active 2,2'-bipyridine (bpy). The reaction of LZnI (L = HC[C(Me)N(2,6-iPr2C6H3)]2) with NaB(C6F5)4 in the presence of bpy yielded [LZn(bpy)][B(C6F5)4] (1), with bpy serving as a neutral ligand, whereas reduction reactions of LZnI with 1 or 2 equiv of KC8 in the presence of bpy gave the radical complex LZn(bpy) (2) and [2.2.2-Cryptand-K][LZn(bpy)] (3), in which bpy either acts as a π-radical anion or a diamagnetic dianion, respectively. The paramagnetic nature of 2 was confirmed via solution magnetic susceptibility measurements, and UV-vis spectroscopy shows that 2 exhibits absorption bands typical for bpy radical species. The EPR spectra of 2 and its deuterated analog 2-d 8 demonstrate that the spin density is localized to the bpy ligand. Density functional theoretical calculations and natural bond orbital analysis were employed to elucidate the electronic structure of complexes 1-3 and accurately reproduced the structural experimental data. It is shown that reduction of the bpy moiety results in a decrease in the ß-diketiminate co-ligand bite angle and elongation of the Zn-N(ß-diketiminate) bonds, which act cooperatively and in synergy with the bpy ligand by decreasing Zn-N(bpy) bond lengths to stabilize the energy of the LUMO.

Hysteretic thermal spin-crossover in heteroleptic Fe(ii) complexes using alkyl chain substituted 2,2'-dipyridylamine ligands.

The alkyl chain carrying ligands N,N-di(pyridin-2-yl)butanamide (LC4) and N,N-di(pyridin-2-yl)decanamide (LC10) were combined with NCS- co-ligands to form the neutral heteroleptic Fe(ii) complexes trans-[FeII(LC4)2(NCS)2] (1C4) and trans-[FeII(LC10)2(NCS)2] (1C10). Variable temperature crystallographic studies revealed that 1C4 is in the orthorhombic space group Pna21 between 85-200 K whereas 1C10 is in the monoclinic space group P21/c between 85-140 K. The average Fe-N bond lengths suggest that at 85 K 1C4 contains LS Fe(ii) centres; however, the ca. 0.18 Å increase in the average Fe-N bond lengths between 85 and 120 K suggests a spin-transition to the HS state occurs within this temperature interval. 1C10 contains LS Fe(ii) centres between 85 and 105 K. Upon warming from 105 to 140 K the average Fe-N bond lengths increase by ca. 0.19 Å, which suggests a spin-transition to the HS state. Solid-state magnetic susceptibility measurements showed that 1C4 undergoes semi-abrupt spin-crossover with T1/2 = 127.5 K and a thermal hysteresis of ca. 13 K whereas, 1C10 undergoes an abrupt spin-crossover with T1/2 = 119.0 K, and is also accompanied by thermal hysteresis of ca. 4 K. The crystallographic and magnetic data show that the length of the complex's alkyl chain substituents can have a large impact on the structure of the crystal lattice as well as a subtle effect on the T1/2 value for thermal spin-crossover.

Use of the TCNQF4 2- Dianion in the Spontaneous Redox Formation of [FeIII (L- )2 ][TCNQF4 ⋠- ].

The reaction of [FeII (L. )2 ](BF4 )2 with Li2 TCNQF4 results in the formation of [FeIII (L- )2 ][TCNQF4 . - ] (1) where L. is the radical ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N-oxide and TCNQF4 is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. This has been characterised by X-ray diffraction, Raman and Fourier transform infrared (FTIR) spectroscopy, variable-temperature magnetic susceptibility, Mössbauer spectroscopy and electrochemistry. X-ray diffraction studies, magnetic susceptibility measurements and Raman and FTIR spectroscopy suggest the presence of low-spin FeIII ions, the anionic form (L- ) of the ligand and the anionic radical form of TCNQF4 ; viz. TCNQF4 . - . Li2 TCNQF4 reduces the [FeII (L. )2 ]2+ dication, which undergoes a reductively induced oxidation to form the [FeIII (L- )2 ]+ monocation resulting in the formation of [FeIII (L- )2 ][TCNQF4 . - ] (1), the electrochemistry of which revealed four well-separated, diffusion-controlled, one-electron, reversible processes. Mössbauer spectroscopy and electrochemical measurements suggest the presence of a minor second species, likely to be [FeII (L. )2 ][TCNQF4 2- ].

Hexahalorhenate(iv) salts of metal oxazolidine nitroxides.

Eight coordination compounds of formulae [FeII(L˙)2][ReIVCl6] (1a), [FeII(L˙)2][ReIVBr6] (1b), [CoII(L˙)2][ReIVCl6]·CH3CN (2a), [CoII(L˙)2][ReIVBr6] (2b), [NiII(L˙)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L˙)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L˙)2][ReIVCl6] (4a) and [CuII(L˙)2][ReIVBr6] (4b), where L˙ is the aminoxyl radical chelating ligand, 4,4'-dimethyl-2,2'-di(2-pyridyl)oxazolidine-N-oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(L˙)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of iron (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggest that the dried samples are best formulated as [NiII(L˙)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms of 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc = 580 Oe, and a remanent magnetisation Mr = 0.21µB, resulting in a canting angle of ∼1.8°. In contrast, 3b(dried) shows no spin-canting behaviour; a maximum in χMvs. T at T = 3 K suggesting long-range antiferromagnetic ordering. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.