Search results for "COORDINATION CHEMISTRY"
showing 10 items of 231 documents
A general diastereoselective synthesis of highly functionalized ferrocenyl ambiphiles enabled on a large scale by electrochemical purification
2017
International audience; A general synthesis of highly functionalized ferrocenes, which include (P,B)- and (N,B)-ambiphiles, has been developed at a multigram scale. Diastereoselective stepwise modification of di-tert-butylated ferrocenes included the unprecedented separation of electroactive species. Bulky alkyl groups on ferrocenes ensure planar chirality of ambiphiles and enforce closer proximity of antagonist Lewis functions.
A robust nanoporous supramolecular metal–organic framework based on ionic hydrogen bonds
2014
International audience; Hydrogen-bond assembly of tripod-like organic cations [H3-MeTrip]3+ (1,2,3-tri(4′-pyridinium-oxyl)-2-methylpropane) and the hexa-anionic complex [Zr2(oxalate)7]6− leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single-crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I2 …
Theoretical Studies of the Reactivity of Cyclopentadienyl Nitrosyl Alkyl Species of Molybdenum and Tungsten
2000
International audience; The reactivity differences observed experimentally for Cp*W(NO)(CH2CMe3)2 and CpMo(NO)(CH2CMe3)2 have been investigated using density functional theory (DFT) techniques. The reactions of the CpW(NO)(CH2) model complex with NH3 and CH4 are more exothermic and have lower activation barriers than the corresponding processes for CpMo(NO)(CH2). The η2(C,H) methane complex CpM(NO)(CH2)(CH4) (M = Mo, W) can undergo two competitive processes: C−H activation to afford CpM(NO)(CH3)2 or loss of methane. The relative barrier heights are almost identical for M = W, whereas the formation of CpM(NO)(CH3)2 is significantly disfavored for M = Mo. The activation of C−H and N−H bonds …
Copper(II) and nickel(II) complexes of pyridylamido hexadentate ligands: chemical speciation and spectroscopic studies
2003
Abstract Two novel potentially hexadentate ligands, 1,10-(2-bis picolinamide)-4,7-diazadecane (pycdpnen) and 1,8-bis(2-picolinamide)-3,6-dioxaoctane (pycdado) have been synthesised as their hydrochloride salt; its protonation constants and the stability constants of the copper(II) and nickel(II) chelates have been determined by potentiometry. Amide groups deprotonation permits the formation of [MLH −1 ] + species in all cases, while only pycdado gives [MLH −2 ] species. The solid complexes of copper and nickel with the neutral and the deprotonated ligands have been synthesised and characterised by IR, UV–Vis and ESR spectroscopy. The amidic groups are coordinated through the oxygen atoms in…
Highly Functionalized Brønsted Acidic/Lewis Basic Hybrid Ferrocene Ligands: Synthesis and Coordination Chemistry
2019
International audience; A general challenging issue in the synthesis of hemilabile ferrocene ligands is the access to highly functionalized ferrocene starting materials. These can bear donor/acceptor atoms, additional functional and structuring spectator substituents, but the preparation of such species poses general synthetic difficulties. We report herein alternative synthetic routes to hybrid ferrocene donors such as tert-butylated phosphanylcarboxylic acids and their corresponding aldehydes. These hybrid ambiphilic species that combine Brønsted-acidic and Lewis-basic functional moieties in their structure were characterized by multinuclear NMR and single-crystal X-ray diffraction analys…
Synthesis, characterisation, and molecular and electronic structure of CpMoCl2(R1C≡CR2) (R1, R2 = Ph, Et, Me): a new class of half-sandwich 17-electr…
2000
International audience; Addition of alkyne to [CpMoCl2]2 affords compounds CpMoCl2(η2-alkyne) (alkyne = EtC[triple bond, length as m-dash]CMe, 1; EtC[triple bond, length as m-dash]CEt, 2; PhC[triple bond, length as m-dash]CMe, 3; PhC[triple bond, length as m-dash]CPh, 4) in good yields. The compounds have been characterised by C,H analyses, IR, EPR and mass spectroscopies, magnetic susceptibility, and cyclic voltammetry. In addition, a single crystal X-ray diffraction analysis has been carried out for compound 4. The alkyne ligand adopts an almost parallel conformation relative to the Cp ring, essentially identical with that of previously reported Nb, Ta, and W analogues. Geometry optimisat…
Organotin(IV) Complexes Containing Sn–O–Se Moieties: A Structural Inventory
2018
This review focuses on organotin compounds exhibiting Sn–O–Se moieties, the molecular structures of which have been previously resolved by single-crystal X-ray diffraction analysis. Three distinct classes of compounds have been identified. Thus, the various modes of coordination of selenite, selenate and organoseleninate anions with tin atoms of organotin(IV) fragments are illustrated and detailed.1 Introduction2 Organotin(IV) Selenite Complexes3 Organotin(IV) Selenate Complexes4 Organotin(IV) Organoseleninate Complexes5 Summary
Rh(I) Coordination Chemistry of Chiral α-Aminophosphine(η6-arene)chromium Tricarbonyl Ligands
2003
The diastereoselective addition of Ph(2)PH to the chiral ortho-substituted eta(6)-benzaldimine complexes (eta(6)-o-X-C(6)H(4)CH=NAr)Cr(CO)(3) (1, X = MeO, Ar = p-C(6)H(4)OMe; 2, X = Cl, Ar = Ph) leads to the formation of the corresponding chiral aminophosphines (alpha-P,N) Ph(2)P-CH(Ar(1))-NHAr(2) (3, Ar(1) = o-C(6)H(4)(OCH(3))[Cr(CO)(3)], Ar(2) = p-C(6)H(4)OCH(3); 4, Ar(1) = o-C(6)H(4)Cl[Cr(CO)(3)], Ar(2) = Ph) in equilibrium with the starting materials. The uncomplexed benzaldimine (o-ClC(6)H(4)CH=NPh), 2', analogously produces an equilibrium amount of the corresponding aminophosphine Ph(2)P-CH(Ar(1))-NHAr(2) (4', Ar(1) = o-C(6)H(4)Cl, Ar(2) = Ph). Depending on the equilibrium constant, t…
Cobalt Corroles with Bis‐Ammonia or Mono‐DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties
2018
International audience; Four bis-ammonia ligated cobalt corroles and four mono-DMSO ligated cobalt corroles with different mesoaryl substituents on the macrocycle (A 2 Band A 3-corroles) were synthesized and investigated as to their electrochemical and spec-troscopic properties under different solution conditions. The complexation energies of the investigated cobalt corroles were theoretically calculated to illustrate the propensity of the cobalt center for pentacoordination or hexa-coordination with various axial ligands (DMSO, CO, py and NH 3). The structure of one hexacoordinate bis-NH 3 cobalt corrole complex was also determined by X-ray diffraction.
High oxidation state aqueous organometallics. Formation and structure of an oxo-centred Cp*MoV trinuclear cation by chemical reduction of Cp*2Mo2O5
2002
International audience; Reduction of Cp*2Mo2O5 by zinc/CF3CO2H in MeOH–H2O yields a salt which is composed of [Cp*3Mo3O4(O2CCF3)3]+ and [Zn2(O2CCF3)6]2− ions after crystallisation from THF–Et2O.