Search results for "Carbene"
showing 10 items of 152 documents
Cooperative N–H bond activation by amido-Ge(ii) cations
2020
N-heterocyclic carbene (NHC) and tertiary phosphine-stabilized germylium-ylidene cations, [R(L)Ge:]+, featuring tethered amido substituents at R have been synthesized via halide abstraction. Characterization in the solid state by X-ray crystallography shows these systems to be monomeric, featuring a two-coordinate C,N- or P,N-ligated germanium atom. The presence of the strongly Lewis acidic cationic germanium centre and proximal amide function allows for facile cleavage of N-H bonds in 1,2-fashion: the products resulting from reactions with carbazole feature a tethered secondary amine donor bound to a three-coordinate carbazolyl-GeII centre. In each case, addition of the components of the N…
Synthesis of copper(II) and gold(III) bis(NHC)-pincer complexes
2016
Abstract CuII and AuIII chlorido complexes bearing the bis(NHC) carbazolide pincer ligand (bimca) were synthesized by transmetallation from the respective lithium complex [Li(bimca)] (NHC=N-heterocyclic carbene). In the case of copper, two different molecular structures were obtained depending on the copper source. With Cu(II) chloride the paramagnetic mononuclear [Cu(bimca)Cl] complex is formed and has been characterized by EPR spectroscopy and X-ray structure analysis, while copper(I) chloride leads under oxidation to a dinuclear structure in which two cationic [CuII(bimca)] moieties are bridged by one chlorido ligand. The positive charge is compensated by the [CuCl2]− counter ion, as pro…
An Entry to Mixed NHC-Fischer Carbene Complexes and Zwitterionic Group 6 Metal Alkenyls
2016
The addition of NHCs to α,β-unsaturated Cr(0) and W(0) (Fischer) carbene complexes is strongly dependent on the electrophilicity of the carbene carbon. Electrophilic alkoxy-carbene complexes quantitatively react with NHCs to yield stable zwitterionic (racemic) Cr(0) - and W(0) -alkenyls with total regio- and E-stereoselectivity. Less electrophilic aminocarbenes react with NHCs to promote the displacement of a CO ligand and yield "mixed" NHC/Fischer biscarbenes in a process that is unprecedented in group 6 metal-carbene chemistry. In fact, the compounds prepared, are some of the scarce examples of Fischer bisylidenes reported in the literature. The electrochemistry of the zwitterionic Cr(0) …
Acylchalcogenourea Complexes of Silver(I)
2016
Acylthio- or acylselenoureas react with silver(I) oxide to form tetranuclear silver(I) complexes containing the deprotonated acylchalcogenourea ligands bound to the silver atoms through the chalcogen and oxygen atoms. These tetrasilver(I) species react with either 4 or 8 equiv. of a phosphine to afford either dinuclear silver(I) phosphine complexes or tetrahedral silver diphosphine complexes. In these compounds, the acylchalcogenourea ligands form six-membered rings by coordinating to the metal atom through the chalcogen and oxygen atoms. In one case, we observed a very rare example of an acylthiourea ligand coordinated through the nitrogen and sulfur atoms to form a four-membered ring. A s…
Higher MLCT lifetime of carbene iron(ii) complexes by chelate ring expansion
2021
Combining strong σ-donating N-heterocyclic carbene ligands and π-accepting pyridine ligands with a high octahedricity in rigid iron(ii) complexes increases the 3MLCT lifetime from 0.15 ps in the prototypical [Fe(tpy)2]2+ complex to 9.2 ps in [Fe(dpmi)2]2+12+. The tripodal CNN ligand dpmi (di(pyridine-2-yl)(3-methylimidazol-2-yl)methane) forms six-membered chelate rings with the iron(ii) centre leading to close to 90° bite angles and enhanced iron-ligand orbital overlap.
Titanocene–gold complexes containing N-heterocyclic carbene ligands inhibit growth of prostate, renal, and colon cancers in vitro
2016
We report on the synthesis, characterization, and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = −OC(O)-p-C6H4-S−) bound to gold(I)−N-heterocyclic carbene fragments through the thiolate group: [(η5 -C5H5)2TiMe(μ-mba)Au(NHC)]. The cytotoxicities of the heterometallic compounds along with those of novel monometallic gold−N-heterocyclic carbene precursors [(NHC)Au(mbaH)] have been evaluated against renal, prostate, colon, and breast cancer cell lines. The highest activity and selectivity and a synergistic effect of the resulting heterometallic species was found for the prostate and colon cancer cell lines. The colocalization of both tita…
Triazole vs. triazolium carbene ligands in the site-selective cyclometallation of o-carboranes by M(iii) (M = Ir, Rh) complexes
2018
Ir(iii) and Rh(iii)-mediated site-selective cage B-H and C-H bond activation in o-carboranylmethyl derivatives has been achieved. The selectivity of the reaction is related to the electron donating properties of the ligand. 1,2,3-Triazole-derivatives use the N2 position of the triazole ring to direct the selective o-carborane B-H bond activation, whereas the corresponding triazolylidene derivatives lead to the cage C-H bond activation with complete site-selectivity.
Reversible Covalent and Supramolecular Functionalization of Water-Soluble Gold(I) Complexes.
2017
The ligation of gold(I) metalloamphiphiles with biomolecules is reported, using water-soluble AuI -N-alkynyl substituted maleimide complexes. For this purpose, two different polar ligands were applied: 1) a neutral, dendritic tetraethylene glycol-functionalized phosphane and 2) a charged, sulfonated N-heterocyclic carbene (NHC). The retro Diels-Alder reaction of a furan-protected maleimide gold(I) complex, followed by cycloaddition with a diene-functionalized biotin under mild conditions leads to a novel gold(I) metalloamphiphile. The strong streptavidin-biotin binding affinity in buffered aqueous solution of the resulting biotin alkynyl gold(I) phosphane conjugate remains intact. The cytot…
Cross-Metathesis/Intramolecular (Hetero-)Michael Addition: A Convenient Sequence for the Generation of Carbo- and Heterocycles
2017
The high stability and functional group compatibility of ruthenium carbene complexes confer them a great ability to catalyze domino processes. For this reason, the combination of metathesis reactions with additional transformations in a domino fashion has been exploited extensively, with the result of expanding the utility of ruthenium carbene complexes beyond that of just olefin metathesis. Among those domino processes, it is worth mentioning the sequence of cross-metathesis/intramolecular Michael addition, which allows for the generation of a wide variety of carbo- and heterocycles in a very simple manner, taking advantage of the benefits of domino reactions. Carbon-, oxygen- and nitrogen…
Remote Control by π-Conjugation of the Emissive Properties of Fischer Carbene-BODIPY Dyads.
2016
The synthesis, structure, and complete characterization of mono- and bimetallic dyads joining Fischer carbene complexes and BODIPY chromophores are reported. In these organometallic species, the Fischer carbene complex is attached to the BODIPY moiety through a p-aminophenyl group linked at the C8 carbon atom of the BODIPY core. The photophysical properties, namely the corresponding UV/vis absorption and emission spectra of these new metal-carbene complexes, are analyzed and discussed. It is found that whereas the absorption of the considered dyads strongly resembles that of the parent 4-anilinyl-substituted BODIPY, the fluorescence emission is significantly reduced in these species, very l…