Search results for "Gand"
showing 10 items of 4024 documents
Half-sandwich complexes of molybdenum-(III), -(IV) and -(V) with P–O and P–N bifunctional ligands Ph2PCH2X (X = 2-oxazolinyl, or C(O)NPh2)
2000
International audience; The reaction of the ligands Ph2PCH2X (X = 2-oxazolinyl, I; or C(O)NPh2, II) with the half-sandwich molybdenum(III) precursors [Mo(η-C5R5)(μ-Cl)2]2 (R = H or Me) has been investigated. Ligand I reacts with both complexes to form the corresponding adducts [Mo(η-C5R5)Cl2(Ph2PCH2C3H4NO)] (R = H, 1; or Me, 2). The reaction between I and [MoCp*Cl4] (Cp* = η-C5Me5) affords [MoCp*Cl4(Ph2PCH2C3H4NO-κ1P)] as a kinetic isomer, which then transforms quantitatively to [MoCp*Cl3(Ph2PCH2C3H4NO-κ2P,N)]+Cl−, 3. Ligand II reacts with [MoCp(μ-Cl)2]2 (Cp = η-C5H5) to afford the adduct [CpMoCl2{Ph2PCH2C(O)NPh2-κ2P,O}], 4, as an equilibrium mixture of two isomers. Longer reaction times in…
Cis- and trans molybdenum oxo complexes of a prochiral tetradentate aminophenolate ligand : Synthesis, characterization and oxotransfer activity
2020
Abstract Reaction of [MoO2Cl2(dmso)2] with the tetradentate O2N2 donor ligand papy [H2papy = N-(2-hydroxybenzyl)-N-(2-picolyl)glycine] leads to formation of the dioxomolybdenum(VI) complex [MoO2(papy)] (1) as a mixture of cis and trans isomers. Recrystallization from methanol furnishes solid cis-1, whereas the use of a dichloromethane-hexane mixture allows for the isolation of the trans-1 isomer. Both isomers have been structurally characterized by X-ray crystallography and the energy difference between the isomeric pair has been investigated by electronic structure calculations. Optimization of two configurational isomers in the gas phase predicts the trans isomer to lie 2.5 kcal/mol lower…
Insight into the Mechanism of Water Adsorption/Desorption in Hydrophilic Viologen-Carboxylate Based PCP
2017
A water stable and highly hydrophilic porous coordination polymer based on viologen-carboxylate type ligand, the 4,4′-bipyridinium,1,1-bis(3-carboxyphenyl) (pc2), is obtained by the solvothermal method: [Cd3(pc2) (BTC)2(H2O)2]·6H2O ([1(H2O)2]·6H2O; BTC3– = 1,3,5-carboxybenzene). Its crystal structure and the ones of two partially dehydrated phases have been determined, allowing insight into the mechanism of water adsorption/desorption of this PCP material. It is shown that the dehydrated compound [1] first adsorbs two water molecules which fill the pores, leading to [1]·2H2O. On the other hand, the partial dehydration of the as-synthesized compound leads to the intermediate phase [1(H2O)]·3…
A family of layered chiral porous magnets exhibiting tunable ordering temperatures.
2013
A simple change of the substituents in the bridging ligand allows tuning of the ordering temperatures, Tc, in the new family of layered chiral magnets A[M(II)M(III)(X2An)3]·G (A = [(H3O)(phz)3](+) (phz = phenazine) or NBu4(+); X2An(2-) = C6O4X2(2-) = 2,5-dihydroxy-1,4-benzoquinone derivative dianion, with M(III) = Cr, Fe; M(II) = Mn, Fe, Co, etc.; X = Cl, Br, I, H; G = water or acetone). Depending on the nature of X, an increase in Tc from ca. 5.5 to 6.3, 8.2, and 11.0 K (for X = Cl, Br, I, and H, respectively) is observed in the MnCr derivative. Furthermore, the presence of the chiral cation [(H3O)(phz)3](+), formed by the association of a hydronium ion with three phenazine molecules, lead…
Equipping metallo-supramolecular macrocycles with functional groups: Assemblies of pyridine-substituted urea ligands
2012
A series of di-(m-pyridyl)-urea ligands were prepared and characterized with respect to their conformations by NOESY experiments and crystallography. Methyl substitution in different positions of the pyridine rings provides control over the position of the pyridine N atoms relative to the urea carbonyl group. The ligands were used to self-assemble metallo-supramolecular M(2)L(2) and M(3)L(3) macrocycles which are generated in a finely balanced equilibrium in DMSO and DMF according to DOSY NMR experiments and ESI FTICR mass spectrometry. Again, crystallography was used to characterize the assemblies. Methyl substitution in positions next to the pyridine nitrogen prevents coordination, while …
Synthesis, Structural and Spectroscopic Characterization of Cr III , Fe III , Co III , Ni II and Cu II Complexes with an Asymmetric 1,3,4‐Thiadiazole…
2016
The reaction of the new asymmetric 1,3,4-thiadiazole-based ligand 2-[(5-ethylthio-1,3,4-thiadiazol-2-yl)hydrazonomethyl]phenol (H1ETHP) with various third-row transition metal salts resulted in the formation of six new mononuclear complexes [Cr(ETHP)2]ClO4 (1), [Fe(ETHP)2][FeCl4] (2), [Co(ETHP)(ETHP–H)] (3), [Ni(ETHP)(H1ETHP)]Cl (4), [Ni(ETHP)(H1ETHP)](ClO4) (5), [Ni(ETHP)(H1ETHP)]Br (6), and one tetranuclear complex [Cu2Cl3(ETHP)(H1ETHP)]2 (7). H1ETHP and all complexes have been analyzed by single crystal X-ray diffraction. Structural analysis of 1–6 reveals complexes of the [ML2]n+-type (n = 0,1), in which the mono anionic ligand ETHP coordinates in a tridentate NNO fashion via its imine,…
Dicopper(II) pyrazolenophanes: Ligand effects on their structures and magnetic properties
2016
Abstract The use of simple pyrazolate anions and related polychelating acyclic or macrocyclic pyrazolate derivatives as bridging ligands, and occasionally additional blocking ligands, has led to the stereospecific Cu II -mediated self-assembly of both homo- and heteroleptic di-μ-pyrazolatodicopper(II) complexes of the metallacyclophane type, so-called dicopper(II) pyrazolenophanes. Besides their unique molecular conformation features and binding abilities toward both neutral molecules and charged anionic species, which have illustrated the putative role of weak intramolecular π–π stacking, hydrogen bonding, and coordinative interactions in the self-assembling process, dicopper(II) pyrazolen…
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…
Synthesis and structural characterization of well-defined bis(oxamato)palladate(II) precatalysts for Suzuki and Heck reactions
2018
Abstract A family of tetra-n-butylammonium salts of bis(oxamato)palladate(II) complexes of formula (n-Bu4N)2[Pd(Lm)2]·pH2O [m = 1–9; L1 = N-phenyloxamate (pma) and p = 2 (1), L2 = N-2-methylphenyloxamate (2-Mepma) and p = 4 (2), L3 = N-4-methylphenyloxamate (4-Mepma) and p = 2 (3), L4 = N-2,3-dimethylphenyloxamate (2,3-Me2pma) and p = 3 (4), L5 = N-2,4-dimethylphenyloxamate (Me2pma) and p = 4 (5), L6 = N-2,5-dimethylphenyloxamate (2,5-Me2pma) and p = 7 (6), L7 = N-3,4-dimethylphenyloxamate (3,4-Me2pma) and p = 6 (7), L8 = N-3,5-dimethylphenyloxamate (3,5-Me2pma) and p = 5 (8)] have been prepared and characterized by spectroscopic methods. The crystal structure of 1 that has been solved by s…
Scalable and Selective Preparation of 3,3′,5,5′-Tetramethyl-2,2′-biphenol
2016
Biphenols are indispensable building blocks in ligand systems for organic catalysis. 3,3′5,5′-Tetramethyl-2,2′-biphenol is a particular versatile motif in different catalytic systems. We developed an easy to perform and scalable process to give access to large quantities of this important building block by the use of selenium dioxide, a common and readily available oxidizer.