Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Yttrium complexes of arsine, arsenide, and arsinidene ligands.

ABSTRACT: Deprotonation of the yttrium-arsine complex [Cp'3Y{As(H)2Mes}] (1) (Cp'=?(5)-C5H4Me, Mes=mesityl) by nBuLi produces the ?-arsenide complex [{Cp'2Y[?-As(H)Mes]}3] (2). Deprotonation of the As-H bonds in 2 by nBuLi produces [Li(thf)4]2[{Cp'2Y(?3-AsMes)}3Li], [Li(thf)4]2[3], in which the dianion 3 contains the first example of an arsinidene ligand in rare-earth metal chemistry. The molecular structures of the arsine, arsenide, and arsinidene complexes are described, and the yttrium-arsenic bonding is analyzed by density functional theory.

SUBMITTER: Pugh T

PROVIDER: S-EPMC4672686 | biostudies-literature | 2015 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Yttrium complexes of arsine, arsenide, and arsinidene ligands.

Pugh Thomas T Kerridge Andrew A Layfield Richard A RA

Angewandte Chemie (International ed. in English) 20150205 14

Deprotonation of the yttrium-arsine complex [Cp'3Y{As(H)2Mes}] (1) (Cp'=η(5)-C5H4Me, Mes=mesityl) by nBuLi produces the μ-arsenide complex [{Cp'2Y[μ-As(H)Mes]}3] (2). Deprotonation of the As-H bonds in 2 by nBuLi produces [Li(thf)4]2[{Cp'2Y(μ3-AsMes)}3Li], [Li(thf)4]2[3], in which the dianion 3 contains the first example of an arsinidene ligand in rare-earth metal chemistry. The molecular structures of the arsine, arsenide, and arsinidene complexes are described, and the yttrium-arsenic bonding ...[more]

PMID: 25655652

Similar Datasets

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs.

Project description:Despite a major expansion of uranium-ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium-arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent-arsenide (ThAsH2), -arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium-arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th-As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

| S-EPMC5347141 | biostudies-literature

C-H bond activation through steric crowding of normally inert ligands in the sterically crowded gadolinium and yttrium (C5Me5)3M complexes.

Project description:Synthesis of the sterically crowded Tris(pentamethylcyclopentadienyl) lanthanide complexes, (C5Me5)3Ln, has demonstrated that organometallic complexes with unconventionally long metal ligand bond lengths can be isolated that provide options to develop new types of ligand reactivity based on steric crowding. Previously, the (C5Me5)3M complexes were known only with the larger lanthanides, La-Sm. The synthesis of even more crowded complexes of the smaller metals Gd and Y is reported here. These complexes allow an evaluation of the size/reactivity correlations previously limited to the larger metals and demonstrate a previously undescribed type of C5Me5-based reaction, namely C-H bond activation. (C5Me5)3Gd, was prepared from GdCl3 through (C5Me5)2GdCl2K(THF)2, (C5Me5)2Gd(C3H5), and [(C5Me5)2Gd][BPh4] and structurally characterized by x-ray crystallography. Although Gd3+ is redox-inactive, (C5Me5)3Gd functions as a reducing agent in reactions with 1,3,5,7-cyclooctatetraene (COT) and triphenylphosphine selenide to make (C5Me5)Gd(C8H8), [(C5Me5)2Gd]2Se2, and [(C5Me5)2Gd]2Se depending on the stoichiometry used. When the analogous synthetic method was attempted with yttrium in arene solvents, the previously characterized (C5Me5)2YR complexes (R=C6H5, CH2C6H5) were isolated instead, i.e., C-H bond activation of solvent occurred. To avoid this problem, (C5Me5)3Y was synthesized in high yield from [(C5Me5)2YH]2 and tetramethylfulvene in aliphatic solvents. Isolated (C5Me5)3Y was found to metalate benzene and toluene with concomitant formation of C5Me5H, a reaction contrary to the normal pKa values of these hydrocarbons. In this case, the normally inert (C5Me5)1- ligand engages in C-H bond activation due to the extreme steric crowding.

| S-EPMC1568909 | biostudies-other

Carbide complexes as ?-acceptor ligands.

Project description:The ?-accepting character of a terminal carbide complex acting as a ligand is demonstrated experimentally and corroborates earlier theoretical predictions. As a result, coordination of a terminal ruthenium carbide complex to electron-rich metal centres is shown to provide a facile and versatile route to carbide-bridged heterometallic complexes. Synthesis, reactivity, spectroscopic and structural characterization are reported for heterobimetallic systems with auxiliary metals from groups 9-11: Rh(i), Ir(i), Pd(ii), Pt(ii), Ag(i), and Au(i) coordinated by [Ru(C)Cl2(PCy3)2] (RuC). This encompasses the first example of a homoleptic carbide-ligated transition metal complex: [{(Cy3P)2Cl2RuC}2Au]+. Kinetics of substitution on Pt(ii) by RuC ranks the carbide complex as having intermediate nucleophilicity. The 13C-NMR signals from the carbide ligands are significantly more shielded in the bridged heterobimetallic complexes than in the parent terminal carbide complex. Structurally, RuC forms very shorts bonds to the heterometals, which supports the notion of the multiple bonded complex acting as a ?-backbonding ligand. Reactions are reported where RuC displaces CO coordinated to Rh(i) and Ir(i). A strong trans influence exerted by RuC indicates it to be a stronger ?-donor than CO. The geometries around the carbide bridges resemble those in complexes of electron-rich metals with carbonyl or bridging nitride-complex-derived ligands, which establishes a link to other strong ?-acceptor ligands.

| S-EPMC5950194 | biostudies-literature

Dibromidobis(triphenyl-arsine)palladium(II).

Project description:In the title compound, [PdBr(2)(C(18)H(15)As)(2)], the Pd(II) ion resides on a centre of symmetry and is coordinated by two As atoms [Pd-As = 2.4184?(3)?Å] and two Br anions [Pd-Br = 2.4196?(3)?Å] in a slightly distorted square-planar geometry [As-Pd-Br = 90.12?(1)°]. The crystal packing exhibits weak inter-molecular C-H?Br inter-actions.

| S-EPMC2968301 | biostudies-literature

Copper Complexes of Multidentate Carboxamide Ligands.

Project description:The copper coordination chemistry of two multidentate carboxamido ligands derived from HL1 (offering two quinolyl and one carboxamide donor) and H4L2 (with two pyridine(dicarboxamido) units linked by naphthalene spacers) was explored. The former was chosen because upon deprotonation it would provide a monoanionic mer-coordinating N-donor set that would model the putative deprotonated form of the His-brace in copper monooxygenases, while the latter was designed to bind two copper ions and enable comparisons to other systems with different ligand spacers. Upon reaction with Cu(I)-mesityl, HL1 yielded a symmetric dimer (L1Cu)2 in which each bis(quinolyl)amide ligand binds via two N-donors to one Cu(I) ion and via the third to the other Cu(I) center. Monomeric Cu(II) complexes [L 1 Cu(H 2 O) 2 ](OTf) and L 1 2 Cu were also characterized. Treatment of H4L2 with Cu(OTf)2 and excess Me4NOH (in CH3CN, pyridine/H2O, or MeOH) yielded complexes with anions of general formula [L 2 Cu 2 (X)]n-, where X = CH3CONH- (n = 1), CO3 2- (n = 2), or MeO- (n = 1). X-ray structures of these complexes revealed the (L2)4- ligand binding to two Cu(II) ions in an open paddle-wheel geometry, with an additional bridging ligand (X) completing the square planar coordination sphere of each metal ion. The open paddlewheel motif differs from the more 'open' puckered geometry seen with related ligands with different spacer units.

| S-EPMC6519725 | biostudies-literature

Electronegativity and location of anionic ligands drive yttrium NMR for molecular, surface and solid-state structures.

Project description:Yttrium is present in various forms in molecular compounds and solid-state structures; it typically provides specific mechanical and optical properties. Hence, yttrium containing compounds are used in a broad range of applications such as catalysis, lasers and optical devices. Obtaining descriptors that can provide access to a detailed structure-property relationship would therefore be a strong base for the rational design of such applications. Towards this goal, 89Y (100% abundant spin ½ nucleus), is associated with a broad range of NMR chemical shifts that greatly depend on the coordination environment of Y, rendering 89Y NMR an attractive method for the characterization of yttrium containing compounds. However, to date, it has been difficult to obtain a direct relationship between 89Y chemical shifts and its coordination environment. Here, we use computational chemistry to model the chemical shift of a broad range of Y(iii) molecular compounds with the goal to reveal the underlying factors that determine the 89Y chemical shift. We show through natural chemical shift (NCS)-analysis that isotropic chemical shifts can easily help to distinguish between different types of ligands solely based on the electronegativity of the central atom of the anionic ligands directly bound to Y(iii). NCS-analysis further demonstrates that the second most important parameter is the degree of pyramidalization of the three anionic ligands imposed by additional neutral ligands. While isotropic chemical shifts can be similar due to compensating effects, investigation of the chemical shift anisotropy (CSA) enables discriminating between the coordination environment of Y.

| S-EPMC7504898 | biostudies-literature

Ru(III) Complexes with Lonidamine-Modified Ligands.

Project description:A series of bifunctional Ru(III) complexes with lonidamine-modified ligands (lonidamine is a selective inhibitor of aerobic glycolysis in cancer cells) was described. Redox properties of Ru(III) complexes were characterized by cyclic voltammetry. An easy reduction suggested a perspective for these agents as their whole mechanism of action seems to be based on activation by metal atom reduction. New compounds demonstrated a more pronounced antiproliferative potency than the parental drug; individual new agents were more cytotoxic than cisplatin. Stability studies showed an increase in the stability of complexes along with the linker length. A similar trend was noted for antiproliferative activity, cellular uptake, apoptosis induction, and thioredoxin reductase inhibition. Finally, at concentrations that did not alter water solubility, the selected new complex evoked no acute toxicity in Balb/c mice.

| S-EPMC8707700 | biostudies-literature

Chiral bisoxazoline ligands designed to stabilize bimetallic complexes.

Project description:Chiral bisoxazoline ligands containing naphthyridine, pyridazine, pyrazole, and phenol bridging units were prepared and shown to form bimetallic complexes with various metal salts. X-ray crystal structures of bis-nickel naphthyridine-bridged, bis-zinc pyridazine-bridged, and bis-nickel as well as bis-palladium pyrazole-bridged complexes were obtained.

| S-EPMC6122208 | biostudies-literature

Au(III) complexes with tetradentate-cyclam-based ligands.

Project description:Chiral cyclam (1,4,8,11-tetraazacyclotetradecane) derivatives were synthesized stepwise from chiral mono-Boc-1,2-diamines and (dialkyl)malonyl dichloride via open diamide-bis(N-Boc-amino) intermediates (65-91%). Deprotection and ring closure with a second malonyl unit afforded the cyclam tetraamide precursors (80-95%). The new protocol allowed the preparation of the target cyclam derivatives (53-59%) by a final optimized hydride reduction. Both the open tetraamine intermediates and the cyclam derivatives successfully coordinated with AuCl3 to give moderate to excellent yields (50-96%) of the corresponding novel tetra-coordinated N,N,N,N-Au(III) complexes with alternating five- and six-membered chelate rings. The testing of the catalytic ability of the cyclam-based N,N,N,N-Au(III) complexes demonstrated high catalytic activity of some complexes in selected test reactions (full conversion in 1-24 h, 62-97% product yields).

| S-EPMC7849238 | biostudies-literature

Dipyridylmethane Ethers as Ligands for Luminescent Ir Complexes.

Project description:This work reports two new cationic heteroleptic cyclometalated iridium complexes, containing ether derivatives of di(pyridin-2-yl)methanol. The new ligands are based on dipyridin-2-ylmethane and are designed to obtain ether-based intermediates with extended electronic conjugation by insertion of π system such as phenyl, allyl and ethynyl. Different synthetic strategies were employed to introduce these units, as molecular wires, between the dipyridin-2-ylmethane chelating portion and the terminal N-containing functional group, such as amine and carbamide. The corresponding complexes show luminescence in the blue region of the spectrum, lifetimes between 0.6 and 2.1 μs, high quantum yield and good electrochemical behavior. The computational description (DFT) of the electronic structure highlights the key role of the conjugated π systems on optical and electrochemical properties of the final products.

| S-EPMC8659258 | 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