Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner.

The reaction of Pd(OAc)2 with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp3 )-H bond activation at one of the CDC methyl side arms. The solid structure of 1 reveals the capability of CDC to facilitate a double dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate π-conjugation within the CDC framework. Such effect maybe also amplified by ligand-ligand interaction. The formation of other gem-bimetallic Pd-Pd, Pd-Au, and Ni-Au provides further structural evidence for this proof-of-concept in selective installation. Structural analysis is supported by computational calculations based on state-of-the-art energy decomposition analysis (EDA) in conjunction with natural orbitals for chemical valence (NOCV) method.

Electrocatalytic Water Reduction Beginning with a {Fe(NO)2}10-Reduced Dinitrosyliron Complex: Identification of Nitrogen-Doped FeO x(OH) y as a Real Heterogeneous Catalyst.

Electron paramagnetic resonance, IR, single-crystal X-ray diffraction, and density functional theory computation reveal that the electronic structure of α-diimine-coordinated {Fe(NO)2}10-reduced dinitrosyliron complexes (DNICs) may best be described as [{Fe(NO)2}10-L•], with the added electron residing mainly on the α-diimine ligand framework. The combination of electrochemistry, gas chromatography, Fourier transform infrared, X-ray photoelectron spectroscopy, and scanning electron microscopy-energy-dispersive X-ray studies demonstrates that the cathodic potential promotes/triggers the transformation of an α-diimine-coordinated {Fe(NO)2}10-reduced DNIC into a particulate deposit on the electrode, and electrodeposited-film electrodes, CFeO and CFeNO, are kinetically dominant electrocatalysts responsible for hydrogen evolution reaction (HER) from water with quantitative Faradaic efficiency. In comparison with the CFeO electrode reaching a current density of 10 mA/cm2 with an overpotential of 333 mV for HER, the nitrogen-doped iron oxide electrode, CFeNO, requires 147 mV of overpotential to achieve a current density of 10 mA/cm2 in a 1 M NaOH aqueous solution. The CFeNO electrode exhibits higher kinetic efficiency (Tafel slope of 59 mV/dec) than the CFeO electrode (Tafel slope of 122 mV/dec) in alkaline conditions. As opposed to high Rct (74.3 Ω) displayed by the CFeO electrode, the smaller charge-transfer resistance ( Rct) of the CFeNO electrode (34.0 Ω) demonstrated that the better HER catalytic activity may be ascribed to the incorporation of nitrogen into iron oxide architecture, which increases the surface roughness and electroconductivity of the CFeNO electrode (56.9% iron content and nitrogen electron-donating effect) and improves HER catalysis by polarizing the incoming water molecule (acting as a proton tray). This result implicates that a (NH4)2SO4-assisted nitrogen-doping strategy is a direct and effective method to realize synergistic regulation of the reaction dynamics, catalytically active sites and electronic conductivity, endowing this nitrogen-doped material CFeNO electrode as a promising HER electrocatalyst under alkaline conditions.

{Fe(NO)(2)(9) Dinitrosyl Iron Complex Acting as a Vehicle for the NO Radical.

To carry and deliver nitric oxide with a controlled redox state and rate is crucial for its pharmaceutical/medicinal applications. In this study, the capability of cationic {Fe(NO)2}9 dinitrosyl iron complexes (DNICs) [(RDDB)Fe(NO)2]+ (R = Me, Et, Iso; RDDB = N,N'-bis(2,6-dialkylphenyl)-1,4-diaza-2,3-dimethyl-1,3-butadiene) carrying nearly unperturbed nitric oxide radical to form [(RDDB)Fe(NO)2(•NO)]+ was demonstrated and characterized by IR, UV-vis, EPR, NMR, and single-crystal X-ray diffractions. The unique triplet ground state of [(RDDB)Fe(NO)2(•NO)]+ results from the ferromagnetic coupling between two strictly orthogonal orbitals, one from Fe dz2 and the other a π*op orbital of a unique bent axial NO ligand, which is responsible for the growth of a half-field transition (ΔMS = 2) from 70 to 4 K in variable-temperature EPR measurements. Consistent with the NO radical character of coordinated axial NO ligand in complex [(MeDDB)Fe(NO)2(•NO)]+, the simple addition of MeCN/H2O into CH2Cl2 solution of complexes [(RDDB)Fe(NO)2(•NO)]+ at 25 °C released NO as a neutral radical, as demonstrated by the formation of [S5Fe(NO)2]- from [S5Fe(µ-S)2FeS5]2-.

Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules.

An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).

Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO2.

A simple and convergent synthetic strategy used to increase the diversity of the carbodicarbene ligand framework through incorporation of unsymmetrical pendant groups is reported. Structural analysis and spectroscopic studies of ligands and their Rh complexes are reported. Reactivity studies reveal carbodicarbenes as competent organocatalysts for amine methylation using CO2 as a synthon. A unique BH-activated boron-carbodicarbene complex was isolated as a reaction intermediate, providing mechanistic insight into the CO2 functionalization process.

Bimetallic nickel aluminum mediated para-selective alkenylation of pyridine: direct observation of eta2,eta1-pyridine Ni(0)-Al(III) intermediates prior to C-H bond activation.

We have presented new amino-NHC Ni-Al complex mediated para C-H bond activation for pyridine and quinolin, and isolated for the first time the intermediate structure of a bimetallic eta(2),eta(1)-pyridine nickel aluminum complex prior to its C-H activation, which serves as key evidence for bimetallic catalysis.

Structural and electronic trends for five coordinate 1(st) row transition metal complexes: Mn(ii) to Zn(ii) captured in a bis(iminopyridine) framework.

The preparation and characterization of a series of divalent 3d transition metal complexes supported by a tridentate planar bis(iminopyridine) ligand are reported. The complexes {2,6-[PhC[double bond, length as m-dash]N(tBu2C6H3)]2C5H3N}MBr2 (M = Mn, Fe, Co, Ni, Cu, Zn), 1-6, were characterized by single crystal X-ray structural studies revealing complexes with pentacoordinate distorted square pyramidal coordination environments. This assembly of complexes provided a unique array for examining the relationship between experimental structure and computed electronic structure. While experimental structural features basically correlated with the Irving-Williams series, some clear deviations were rationalized through the computational analysis. A balance of bis(imino)pyridine/metal with bonding/antibonding π interactions was used to explain the divergent directions of Fe(ii)-N and Co(ii)-N bond lengths. Similarly, orbital details were used to justify the opposing change in Cu-Brap and Cu-Brbas bond lengths. Furthermore, computational analysis provided a unique method to document a surprising low bond order for the M-N bonds of bis(imino)pyridine ligand in this series.

New members of a class of dinitrosyliron complexes (DNICs): the characteristic EPR signal of the six-coordinate and five-coordinate {Fe(NO)2}9 DNICs.

Compared to the tetrahedral {Fe(NO)(2)}(9) dinitrosyliron complexes (DNICs) [(L)(2)Fe(NO)(2)](-) (L=SR, imidazolate) displaying EPR signal g=2.03, the newly synthesized six-/five-coordinate {Fe(NO)(2)}(9) DNICs [(TPA)Fe(NO)(2)][BF(4)] (1-TPA) (TPA=2-[CH(2)-C(5)H(4)N](3)N), [((iPr)PDI)Fe(NO)(2)][BF(4)] (2-(iPr)PDI) ((iPr)PDI=2,6-[2,6-(i)Pr(2)-C(6)H(3)N=CMe](2)C(5)H(3)N) and [(PyImiS)Fe(NO)(2)] (4-PyImiS) (PyImiS=2-[2-(C(5)H(4)N)CMe=N]C(6)H(4)S) exhibit the distinct EPR signal g=2.015-2.018. The Fe K-edge pre-edge energy (7113.4-7113.6eV) derived from the 1s→3d transition in the octahedral and square-pyramidal environment of the Fe center, falling within the range of 7113.4-7113.8eV for the tetrahedral {Fe(NO)(2)}(9) DNICs, implicates that the iron cores of DNICs 1-TPA, 2-(iPr)PDI and 4-PyImiS are tailored to minimize the electronic changes accompanying changes in coordination geometry. In contrast to the thermally stable 1-TPA, 2-(iPr)PDI and 4-PyImiS, the spontaneous transformation of the proposed thermally unstable five-coordinate {Fe(NO)(2)}(9) DNIC [(PyPepS-H)Fe(NO)(2)](-) (6-PyPepS) (PyPepS-H=[SC(6)H(4)-o-NC(O)(C(5)H(4)N)]) into the {Fe(NO)}(7)-{Fe(NO)}(7) [(µ-PyPepS-H)Fe(NO)](2) (7) along with release of nitroxyl demonstrates that the distinct electron-donating ability of the coordinated ligands ([PyPepS-H]>[PyImiS]~[TPA]>[(iPr)PDI]) regulates the stability and geometric structure of {Fe(NO)(2)}(9) DNICs. This study also shows the aspect of how the geometric structure of {Fe(NO)(2)}(9) DNICs imposed by the electron-donating ability and conformation of the coordinated ligands (tridentate [(iPr)PDI] vs tridentate [PyImiS] vs tetradentate [TPA] vs tridentate [PyPepS-H] vs bidentate [SC(6)H(4)-o-NC(O)Ph](2-)) regulates the Fe-NO bonding of {Fe(NO)(2)}(9) DNICs and presumably the release of nitroxyl from DNICs.

Preparation and characterization of amino-linked heterocyclic carbene palladium, gold, and silver complexes and their use as anticancer agents that act by triggering apoptotic cell death.

Transition metal complexes bearing amino linked N-heterocyclic carbenes (NHC) were prepared and evaluated for their antiproliferative activities in human cancer cells. The optimum antiproliferative activity, observed for the gold complex 3 in U-87 MG cells, was found to involve S-phase arrest of the cell cycle. The results indicate that 3 induces apoptosis through a p53-bak pathway, a finding that could serve as a new strategy to reduce the resistance of cancer cells to p53-induced apoptosis.