Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Group 13 Element Trihalide Complexes of Anionic N-Heterocyclic Carbenes.

ABSTRACT: A series of group 13 complexes of the general type [{(WCA-IDipp)EX3 }Li(solv)] (E=B, Al, Ga, In; X=Cl, Br) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA-IDipp, WCA=B(C6 F5 )3 and IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by the reaction of the respective group 13 trihalides (EX3 ) with the lithium salt [(WCA-IDipp)Li???toluene]. The molecular structures of the BBr3 , AlCl3 , AlBr3 , GaCl3 and InCl3 adducts were established by X-ray diffraction analyses, revealing the formation of coordination polymers linked by halide-lithium interactions, except for the indium derivative, which consists of isolated [Li(THF)4 ]+ and [(WCA-IDipp)InCl3 ]- ions in the solid state.

SUBMITTER: Ho LP

PROVIDER: S-EPMC7154526 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Group 13 Element Trihalide Complexes of Anionic N-Heterocyclic Carbenes.

Ho Luong Phong LP Anders Lisa L Tamm Matthias M

Chemistry, an Asian journal 20200220 6

A series of group 13 complexes of the general type [{(WCA-IDipp)EX3 }Li(solv)] (E=B, Al, Ga, In; X=Cl, Br) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA-IDipp, WCA=B(C6 F5 )3 and IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by the reaction of the respective group 13 trihalides (EX3 ) with the lithium salt [(WCA-IDipp)Li ⋅ toluene]. The molecular structures of the B ...[more]

PMID: 32011782

Similar Datasets

Halogen Complexes of Anionic N-Heterocyclic Carbenes.

Project description:The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating anionic borate moiety (WCA-NHC) reacted with iodine, bromine, or CCl4 to afford the zwitterionic 2-halogenoimidazolium borates (WCA-NHC)X (X=I, Br, Cl; WCA=B(C6 F5 )3 , B{3,5-C6 H3 (CF3 )2 }3 ; NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, or NHC=IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene). The iodine derivative (WCA-IDipp)I (WCA=B(C6 F5 )3 ) formed several complexes of the type (WCA-IDipp)I⋅L (L=C6 H5 Cl, C6 H5 Me, CH3 CN, THF, ONMe3 ), revealing its ability to act as an efficient halogen bond donor, which was also exploited for the preparation of hypervalent bis(carbene)iodine(I) complexes of the type [(WCA-IDipp)I(NHC)] and [PPh4 ][(WCA-IDipp)I(WCA-NHC)] (NHC=IDipp, IMes). The corresponding bromine complex [PPh4 ][(WCA-IDipp)2 Br] was isolated as a rare example of a hypervalent (10-Br-2) system. DFT calculations reveal that London dispersion contributes significantly to the stability of the bis(carbene)halogen(I) complexes, and the bonding was further analyzed by quantum theory of atoms in molecules (QTAIM) analysis.

| S-EPMC7986712 | biostudies-literature

Heterobimetallic Coinage Metal-Ruthenium Complexes Supported by Anionic N-Heterocyclic Carbenes.

Project description:The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating borate moiety (WCA-NHC, WCA=B(C6 F5 )3 , NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were used for the preparation of silver(I) or copper(I) WCA-NHC complexes. While the reactions in THF with AgCl or CuCl afforded anionic mono- and dicarbene complexes with solvated lithium counterions [Li(THF)n ]+ (n=3, 4), the reactions in toluene proceeded with elimination of LiCl and formation of the neutral phosphine and arene complexes [(WCA-NHC)M(PPh3 )] and [(WCA-NHC)M(η2 -toluene)] (M=Ag, Cu). The latter were used for the preparation of chlorido- and iodido-bridged heterobimetallic Ag/Ru and Cu/Ru complexes [(WCA-NHC)M(μ-X)2 Ru(PPh3 )(η6 -p-cymene)] (M=Ag, Cu, X=Cl; M=Ag, X=I). Surprisingly, these complexes resisted the elimination of CuCl, AgCl, or AgI, precluding WCA-NHC transmetalation.

| S-EPMC8597159 | biostudies-literature

Rhodium and Iridium Complexes of Anionic Thione and Selone Ligands Derived from Anionic N-Heterocyclic Carbenes.

Project description:The lithium salts of anionic N-heterocyclic thiones and selones [{(WCA-IDipp)E}Li(toluene)] (1: E=S; 2: E=Se; WCA=B(C6 F5 )3 , IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene), which contain a weakly coordinating anionic (WCA) borate moiety in the imidazole backbone were reacted with Me3 SiCl, to furnish the silylated adducts (WCA-IDipp)ESiMe3 (3: E=S; 4: E=Se). The reaction of the latter with [(η5 -C5 Me5 )MCl2 ]2 (M=Rh, Ir) afforded the rhodium(III) and iridium(III) half-sandwich complexes [{(WCA-IDipp)E}MCl(η5 -C5 Me5 )] (5-8). The direct reaction of the lithium salts 1 and 2 with a half or a full equivalent of [M(COD)Cl]2 (M=Rh, Ir) afforded the monometallic complexes [{(WCA-IDipp)E}M(COD)] (9-12) or the bimetallic complexes [μ2 -{(WCA-IDipp)E}M2 (COD)2 (μ2 -Cl)] (13-16), respectively. The bonding situation in these complexes has been investigated by means of density functional theory (DFT) calculations, revealing thiolate or selenolate ligand character with negligible metal-chalcogen π-interaction.

| S-EPMC9305287 | biostudies-literature

Sulfur, mercury, and boron adducts of sydnone imine derived anionic N-heterocyclic carbenes.

Project description:The sydnone imines (5-benzoylimino)-3-(2-methoxyphenyl)-sydnone imine and molsidomine were deprotonated at C4 to give sydnone imine anions which can be represented as anionic N-heterocyclic carbenes, respectively. Trapping reactions with sulfur gave unstable sydnone imine sulfides which were stabilized by the formation of methyl thioethers, methyl sulfoxides, gold complexes [(PPh3)Au-S-sydnone imine] and a bis(ligand) mercury(ii) complex. The latter possesses a tetrahedral coordination of the mercury central atom to the sulfur atoms with the N6 nitrogen atoms coordinating as neutral ligands. Water converted the molsidomine anion into ethyl(2-morpholino-2-thioxoacetyl)carbamate. Mercury(ii)chloride and triphenylborane were employed to trap the sydnone imine carbenes as mercury complexes as well as BPh3 adducts.

| S-EPMC9060589 | biostudies-literature

From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer.

Project description:The mesomeric betaine imidazolium-1-ylphenolate forms a borane adduct with tris(pentafluorophenyl)borane by coordination with the phenolate oxygen, whereas its NHC tautomer 1-(2-phenol)imidazol-2-ylidene reacts with (triphenylphosphine)gold(I) chloride to give the cationic NHC complex [Au(NHC)2][Cl] by coordination with the carbene carbon atom. The anionic N-heterocyclic carbene 1-(2-phenolate)imidazol-2-ylidene gives the complexes [K][Au(NHC-)2], [Rh(NHC-)3] and [Ni(NHC-)2], respectively. Results of four single crystal analyses are presented.

| S-EPMC5238575 | biostudies-literature

Insights into the Factors Controlling the Origin of Activation Barriers in Group 13 Analogues of the Four-Membered N-Heterocyclic Carbenes.

Project description:The mechanisms of C-H bond insertion and alkene cycloaddition were investigated theoretically using five model systems: group 13 analogues of the four-membered nucleophilic N-heterocyclic carbenes (NHCs) (1E; E = group 13 element). The theoretical findings indicate that, except for 1B with H2C=CH2, these four-membered NHCs undergo insertion and [1 + 2] cycloaddition reactions with difficulty because their activation barriers are quite high (31 kcal/mol). The theoretically confirmed chemical inertness of the four-membered NHCs 1Ga and 1In might explain why they have been experimentally detected at room temperature. Additionally, our theoretical observations indicate that the reactivity of these four-membered NHCs featuring a central group 13 element follows the order 1B ≫ 1Al > 1Ga > 1In > 1Tl. The theoretical examination suggests that the smaller the atomic radius of the central group 13 element in the four-membered NHC analogue is, the larger the aromaticity of this carbenic molecule is, the higher the basicity of this carbenic molecule in nature is, the larger its nucleophilic attack on other oncoming molecules is, the smaller the barrier heights of its C-H bond insertion and [1 + 2] cycloaddition reactions will be, the higher its exothermicities for these products will be, and thus, the greater its reactivity will be. Moreover, the present theoretical findings reveal that the reactivity of 1B is governed by its highest occupied molecular orbital, a nonbonding sp2 lone pair orbital. In contrast, the reactivity of the four heavier 1E' (E' = Al, Ga, In, and Tl) molecules is mainly determined by their lowest unoccupied molecular orbital, a vacant p-π orbital. The conclusions gained from this study allow many predictions to be made.

| S-EPMC8412915 | biostudies-literature

Sydnone Methides-A Forgotten Class of Mesoionic Compounds for the Generation of Anionic N-Heterocyclic Carbenes.

Project description:Sydnone methides are described from which only one single example has been mentioned in the literature so far. Their deprotonation gave anions which can be formulated as π-electron rich anionic N-heterocyclic carbenes. Sulfur and selenium adducts were stabilized as their methyl ethers, and mercury, gold as well as rhodium complexes of the sydnone methide carbenes were prepared. Sydnone methide anions also undergo C-C coupling reactions with 1-fluoro-4-iodobenzene under Pd(PPh3 )4 and CuBr catalysis. 77 Se NMR resonance frequencies and 1 JC4-Se as well as 1 JC4-H coupling constants have been determined to gain knowledge about the electronic properties of the anionic N-heterocyclic carbenes. The carbene carbon atom of the sydnone methide anion 3 j resonates at δ=155.2 ppm in 13 C NMR spectroscopy at -40 °C which is extremely shifted upfield in comparison to classical N-heterocyclic carbenes.

| S-EPMC8456854 | biostudies-literature

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent.

Project description:Mercury(II) complexes (Me-maloNHCDipp)HgCl (1b), (t-Bu-maloNHCDipp)HgCl (2b) and (t-Bu-maloNHCDipp)HgMe (2c) supported by anionic N-heterocyclic carbenes have been obtained in good yields from the reaction of the potassium salt of N-heterocyclic carbene ligand precursors and mercury(II) salts, HgCl2 and MeHgI. These molecules have been characterized by 1H-NMR, 13C-NMR and IR spectroscopy and elemental analysis. X-ray crystal structures of 1b and 2b are also presented. Interestingly, complex 1b is polymeric {(Me-maloNHCDipp)HgCl}n in the solid state, as a result of inter-molecular Hg-O contacts, and features rare three coordinate mercury sites with a T-shaped arrangement, whereas the (t-Bu-maloNHCDipp)HgCl (2b) is monomeric and has a linear, two-coordinate mercury center. The formation of T-shaped structure and the aggregation of complex 1b is attributable to the reduced steric demand of the N-heterocyclic carbene ligand backbone substituent.

| S-EPMC7464600 | biostudies-literature

Mechanistic insights into the insertion and addition reactions of group 13 analogues of the six-membered N-heterocyclic carbenes: interplay of electrophilicity, basicity, and aromaticity governing the reactivity.

Project description:Three fundamental concepts (aromaticity/basicity/electrophilicity), being heavily used in modern chemistry, have been applied in this work to study the chemical reactivity of six-membered-ring group 13 N-heterocyclic carbenes (G13-6-Rea; G13 = group 13 elements) using density functional theory (BP86-D3(BJ)/def2-TZVP). G13-6-Rea is isolobal to benzene. Two model reactions have been used in the present study: the insertion reaction of G13-6-Rea with methane and the [1 + 2] cycloaddition reaction of G13-6-Rea with ethene. Our theoretical analysis reveals that the chemical reactivity of B-6-Rea, Al-6-Rea, and Ga-6-Rea is governed by their HOMO (the sp2-σ lone pair orbital on the G13 element), and thus they can be considered nucleophiles. Conversely, the chemical behavior of In-6-Rea and Tl-6-Rea is determined by their LUMO (the vacant p-π orbital on the G13 element), and thus they can be considered electrophiles. On the basis of the VBSCD (valence bond state correlation diagram) model and ASM (activation strain model), this theoretical evidence demonstrates that the origin of activation barriers for the above model reactions is due to the atomic radius of the pivotal group 13 element in the six-membered-ring of G13-6-Rea. Accordingly, our theoretical conclusions suggest that the lower the atomic number and the smaller the atomic radius of the G13 atom, the higher the aromaticity of the six-membered-ring of G13-6-Rea and the smaller the singlet-triplet energy splitting ΔE st of this N-heterocyclic carbene analogue, which will facilitate its chemical reactions. The theoretical findings originating from this study allow many predictions in experiments to be made.

| S-EPMC9033959 | biostudies-literature

N-Heterocyclic Carbene Organocatalysis: With or Without Carbenes?

Project description:In this work the mechanism of the aldehyde umpolung reactions, catalyzed by azolium cations in the presence of bases, was studied through computational methods. Next to the mechanism established by Breslow in the 1950s that takes effect through the formation of a free carbene, we have suggested that these processes can follow a concerted asynchronous path, in which the azolium cation directly reacts with the substrate, avoiding the formation of the carbene intermediate. We hereby show that substituting the azolium cation, and varying the base or the substrate do not affect the preference for the concerted reaction mechanism. The concerted path was found to exhibit low barriers also for the reactions of thiamine with model substrates, showing that this path might have biological relevance. The dominance of the concerted mechanism can be explained through the specific structure of the key transition state, avoiding the liberation of the highly reactive, and thus unstable carbene lone pair, whereas activating the substrate through hydrogen-bonding interactions. Polar and hydrogen-bonding solvents, as well as the presence of the counterions of the azolium salts facilitate the reaction through carbenes, bringing the barriers of the two reaction mechanisms closer, in many cases making the concerted path less favorable. Thus, our data show that by choosing the exact components in a reaction, the mechanism can be switched to occur with or without carbenes.

| S-EPMC7496998 | 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