Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis and reactivity of a tris(carbene) zinc chloride complex.

ABSTRACT: The [^PhB(^tBuIm)₃]^1- ligand has gained increased attention since it was first reported in 2006 due to its ability to stabilize highly reactive first row transition metal complexes. In this work, we investigate the coordination chemistry of this ligand with redox-inert zinc to understand how a zinc metal center behaves in such a strong coordinating environment. The ^PhB(^tBuIm)₃ZnCl (1) complex can be formed via deprotonation of [^PhB(^tBuIm)₃][OTf]₂ followed by the addition of ZnCl₂. Salt metathesis reaction with nucleophilic n-BuLi yields the highly carbon-rich zinc coordination complex ^PhB(^tBuIm)₃ZnBu (2) with three carbene atom donors and one carbanion donor. In contrast, reaction of complex 1 with a less nucleophilic polysulfide reagent, [K.18-C-6]₂[S₄], leads to the formation of a tetrahedral zinc tetrasulfido complex via protonation of one carbene donor to form ^PhB(^tBuIm)₂(^tBuImH)Zn(κ²-S₄) (3).

SUBMITTER: Sherbow TJ

PROVIDER: S-EPMC9673275 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis and reactivity of a tris(carbene) zinc chloride complex.

Sherbow Tobias J TJ Li Keyan K Zakharov Lev N LN Pluth Michael D MD

Dalton transactions (Cambridge, England : 2003) 20221004 38

The [PhB(tBuIm)3]1- ligand has gained increased attention since it was first reported in 2006 due to its ability to stabilize highly reactive first row transition metal complexes. In this work, we investigate the coordination chemistry of this ligand with redox-inert zinc to understand how a zinc metal center behaves in such a strong coordinating environment. The PhB(tBuIm)3ZnCl (1) complex can be formed < ...[more]

PMID: 36074723

Similar Datasets

Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex.

Project description:We report the uranium(VI) carbene imido oxo complex [U(BIPM(TMS))(NMes)(O)(DMAP)2] (5, BIPM(TMS) = C(PPh2 NSiMe3)2; Mes = 2,4,6-Me3C6H2; DMAP = 4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM(TMS))(O)2(DMAP)2] (6).

| S-EPMC4464547 | biostudies-literature

Molecular and Crystal Structure of a Chitosan-Zinc Chloride Complex.

Project description:We determined the molecular and packing structure of a chitosan-ZnCl2 complex by X-ray diffraction and linked-atom least-squares. Eight D-glucosamine residues-composed of four chitosan chains with two-fold helical symmetry, and four ZnCl2 molecules-were packed in a rectangular unit cell with dimensions a = 1.1677 nm, b = 1.7991 nm, and c = 1.0307 nm (where c is the fiber axis). We performed exhaustive structure searches by examining all of the possible chain packing modes. We also comprehensively searched the positions and spatial orientations of the ZnCl2 molecules. Chitosan chains of antiparallel polarity formed zigzag-shaped chain sheets, where N2···O6, N2···N2, and O6···O6 intermolecular hydrogen bonds connected the neighboring chains. We further refined the packing positions of the ZnCl2 molecules by theoretical calculations of the crystal models, which suggested a possible coordination scheme of Zn(II) with an O6 atom.

| S-EPMC8229668 | biostudies-literature

Carbene transfer reactivity from a nickelacyclobutane.

Project description:A formal carbene-transfer reaction from an isolated nickelacyclobutane to an isocyanide to form a ketenimine is reported. DFT calculations support a stepwise 1,1-insertion/fragmentation pathway without a carbene intermediate. This unusual reactivity suggests a potential new role as "carbene reservoir" for nickelacyclobutanes, which are typically seen as intermediates in catalytic cyclopropanation.

| S-EPMC11456996 | biostudies-literature

Tris(1,10-phenanthroline-?N,N')zinc(II) chloride 2-phenyl-4-selenazole-5-car-box-yl-ate decahydrate.

Project description:The asymmetric unit of the title salt, [Zn(C(12)H(8)N(2))(3)](C(10)H(6)NO(2)Se)Cl·10H(2)O, contains a [Zn(phen)(3)](2+) cation (phen is 1,10-phenanthroline), uncoordinated chloride and 2-phenyl-4-selenazole-5-carboxyl-ate anions and ten uncoord-in-ated water mol-ecules. The central Zn(II) ion is six-coordinated by six N atoms from three phen ligands in a distorted octa-hedral geometry. An extensive O-H?O, O-H?N and O-H?Cl hydrogen-bonding network stabilizes the crystal structure.

| S-EPMC3051608 | biostudies-literature

Carbene Complexes in the Synthesis of Complex Natural Products: Total Synthesis of the Calphostins.

Project description: Not available

| S-EPMC3548573 | biostudies-literature

Carbene reactivity from alkyl and aryl aldehydes.

Project description:Carbenes are highly enabling reactive intermediates that facilitate a diverse range of otherwise inaccessible chemistry, including small-ring formation and insertion into strong σ bonds. To access such valuable reactivity, reagents with high entropic or enthalpic driving forces are often used, including explosive (diazo) or unstable (gem-dihalo) compounds. Here, we report that common aldehydes are readily converted (via stable α-acyloxy halide intermediates) to electronically diverse (donor or neutral) carbenes to facilitate >10 reaction classes. This strategy enables safe reactivity of nonstabilized carbenes from alkyl, aryl, and formyl aldehydes via zinc carbenoids. Earth-abundant metal salts [iron(II) chloride (FeCl2), cobalt(II) chloride (CoCl2), copper(I) chloride (CuCl)] are effective catalysts for these chemoselective carbene additions to σ and π bonds.

| S-EPMC9439075 | biostudies-literature

Pnictogen Bonding at the Core of a Carbene-Stiborane-Gold Complex: Impact on Structure and Reactivity.

Project description:Our interest in the design of ambiphilic ligands and their coordination to gold has led us to synthesize an indazol-3-ylidene gold chloride complex functionalized at the 4-position of the indazole backbone by a stibine functionality. The antimony center of this new complex cleanly reacts with o-chloranil to afford the corresponding stiborane derivative. Structural analysis indicates that the stiborane coordination environment is best described as a distorted square pyramid whose open face is oriented toward the gold center, allowing for the formation of a long donor-acceptor, or pnictogen, Au → Sb bonding interaction. The presence of this interaction, which has been probed computationally, is also manifested in the enhanced catalytic activity of this complex in the cyclization of N-propargyl-4-fluorobenzamide.

| S-EPMC11481098 | biostudies-literature

Synthesis, Structure, and Reactivity of Molybdenum- and Tungsten-Indane Complexes with Tris(pyrazolyl)borate Ligand.

Project description:The reaction of molybdenum complexes with a tris(pyrazolyl)borate ligand (Et4N[TpMo(CO)3] and Et4N[Tp*Mo(CO)3] (Tp = hydridotris(pyrazolyl)borate, Tp* = hydridotris(3,5-dimethylpyrazolyl)borate)) and InBr3 at a 1:1 molar ratio afforded molybdenum-indane complexes (Et4N[TpMo(CO)3(InBr3)] 1 and Et4N[Tp*Mo(CO)3(InBr3)] 2). In addition, tungsten-indane complexes, Et4N[TpW(CO)3(InBr3)] 3 and Et4N[Tp*W(CO)3(InBr3)] 4, were obtained by the reaction of corresponding tungsten complexes. Complex 4 reacted with H2O to form the hydrido complex Tp*W(CO)3H, in which the W-In bond was cleaved. On the other hand, 4 reacted with three equiv. of AgNO3 to form Et4N[Tp*W(CO)3{In(ONO2)}] 5, in which three substituents on the In were exchanged while retaining the W-In dative bond. Complexes 1-5 were fully characterized using NMR measurements and elemental analyses, and the structures of 1-5 and Et4N[Tp*W(CO)3] were determined via X-ray crystallography. These are the first examples of mononuclear molybdenum- and tungsten-indane complexes with Mo-In and W-In dative bonds.

| S-EPMC10893353 | biostudies-literature

Synthesis, Luminescence, and Electrochemistry of Tris-Chelate Platinum(IV) Complexes with Cyclometalated N-Heterocyclic Carbene Ligands and Aromatic Diimines.

Project description:Dicationic, C2-symmetrical, tris-chelate Pt(IV) complexes of general formula [Pt(trz)2(N∧N)](OTf)2, bearing two cyclometalated 4-butyl-3-methyl-1-phenyl-1H-1,2,3-triazol-5-ylidene (trz) ligands and one aromatic diimine [N∧N = 2,2'-bipyridine (bpy, 2), 4,4'-di-tert-butyl-2,2'-bipyridine (dbbpy, 3), 4,4'-dimethoxi-2,2'-bipyridine (dMeO-bpy, 4), 1,10-phenanthroline (phen, 5), 4,7-diphenyl-1,10-phenanthroline (bphen, 6), dipyrido[3,2-a:2',3'-c]phenazine (dppz, 7), or 2,3-diphenylpyrazino[2,3-f][1,10]phenanthroline (dpprzphen, 8)] are obtained through chloride abstraction from [PtCl2(trz)2] (1) using AgOTf in the presence of the corresponding diimine. Complexes 2-4 show long-lived phosphorescence from 3LC excited states involving the diimine ligand, with quantum yields that reach 0.18 in solution and 0.58 in the solid matrix at room temperature for 3. Derivatives with more extended aromatic systems show dual phosphorescent/fluorescent emissions (5, 6) or mainly fluorescence (7, 8) in solution. Comparisons with similar complexes bearing cyclometalated 2-arylpyridines instead of aryl-N-heterocyclic carbenes indicate that the {Pt(trz)2} subunit is crucial to enable efficient emissions from diimine-centered excited states. It is also shown that the introduction of protective bulky substituents on the diimine, such as the tert-butyl groups in 3, is a key strategy to reach higher emission efficiencies. The new compounds represent rare examples of luminescent Pt(IV) complexes that show quasi-reversible one-electron reductions, indicating an unusually high redox stability.

| S-EPMC11688666 | biostudies-literature

Isolation of chloride- and hydride-bridged tri-iron and -zinc clusters in a tris(β-oxo-δ-diimine) cyclophane ligand.

Project description:A cyclophane ligand (H6L) bearing three β-oxo-δ-diimine arms and the corresponding tri-iron and -zinc complexes in which the metal ions are bridged by either chlorides, viz. Fe3Cl3(H3L) (1) and Zn3Cl3(H3L) (2), or hydrides, viz. Fe3H3(H3L) (3), Zn3H3(H3L) (4), were synthesized and characterized. 1 adopts a chair-shaped C3v-symmetric [Fe3(μ-Cl)3]3+ cluster wherein only one hemisphere of the ligand is metallated and the other three ketoimine sites remain protonated as evidenced by single crystal X-ray diffraction and vibrational and NMR spectroscopic analyses. 3 and 4 were synthesized by substitution of the bridging chlorides in 1 and 2 using KBEt3H and are accessed with retention of the three protonated ketoimine sites.

| S-EPMC6610688 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data