Synthesis, structure, solution chemistry and the electronic effect of para substituents on the vanadium center in a family of mixed-ligand [(VO)-O-V(ONO)(ON)] compexes

Four tridentate dibasic ONO donor hydrazone ligands derived from the condensation of benzoylhydrazine with either 2-hydroxyacetophenone or its para substituted derivatives (H2L1-4, general abbreviation H2L) have been used as primary ligands and 8-hydroxyquinoline (Hhq, a bidentate monobasic ON donor species) has been used as auxiliary ligand. The reaction of [(VO)-O-IV(acac)21 with H2L in methanol followed by the addition of Hhq in equimolar ratio under aerobic condition afforded the mixed-ligand oxovanadium(V) complexes of the type [(VO)-O-V(L)(hq)] (1-4) in excellent yield. The X-ray structure of the compound [(VO)-O-V(L-4)(hq)] (4) indicates that the H2L4 ligand is bonded with vanadium meridionally in a tridentate dinegative fashion through its deprotonated phenolic-O, deprotonated enolic-O and imine-N atoms. The V-O bond length order is: oxo < phenolato < enolato. H-1 NMR spectra of 4 in CDCl3 solution indicates that it's solid-state structure is retained in solution. Complexes are diamagnetic and exhibit only ligand to metal charge transfer (LMCT) transition band near 530 nm in CH2Cl2 solution in addition to intra-ligand pi-pi* transition band near 335 rim and they display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. lambda(max) (for LMCT transition) and the reduction peak potential (E-p(c)) values of the complexes are found to be linearly related with the Hammett (sigma) constants of the substituents in the aryloxy ring of the hydrazone ligands. lambda(max) and E-p(c) values show large dependence d lambda(max)/d sigma = 32.54 nm and dE(p)(c)/d sigma = 0.19 V, respectively, on the Hammett constant. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis, crystal structure and reactivity of copper(II) complexes of tetradentate N2S2 donor ligands

Two new hexa-coordinated mononuclear copper(II) complexes of two ligands L-1 and L-2 containing NSSN donor sets formulated as [Cu(L)(H2O)(2)](NO3)(2) [1a, L = 1,2-bis(2-pyridylmethylthio)ethane (L-1), 1b L = 1,3-bis(2-pyridyl-methylthio)propane (L-2)] were synthesized and characterized by physico-chemical and spectroscopic methods. In 1a the single crystal X-ray crystallography analysis showed a distorted octahedral geometry about copper(II) ion. The crystal packing evidences pairs of complexes arranged about a center of symmetry and connected through a H-bond occurring between aquo ligands and nitrate anions. On reaction with chloride and pseudohalides (N-3(-) and SCN-), in acetonitrile at ambient temperature. complexes 1 changed to monocationic penta-coordinated mononuclear copper(H) species formulated as [Cu(L)(Cl)]NO3 (2), [Cu(L)(N-3)]NO3 (3). and [Cu(L)(SCN)]NO3 (4). These copper(II) complexes have been isolated in pure form from the reaction mixtures and characterized by physico-chemical and spectroscopic tools. The solid-state structure of 2a, established by X-ray crystallography, shows a trigonal bipyramidal geometry about the metal ion with a trigonality index (tau) of 0.561. (C) 2009 Elsevier B.V. All rights reserved.

A novel heteroditopic terpyridine-pincer ligand as building block for mono- and heterometallic Pd(II) and Ru(II) complexes

A palladium-catalyzed Stille coupling reaction was employed as a versatile method for the synthesis of a novel terpyridine-pincer (3, TPBr) bridging ligand, 4'-{4-BrC6H2(CH2NMe2)(2)-3,5}-2,2':6',2 ''-terpyridine. Mononuclear species [PdX(TP)] (X = Br, Cl), [Ru(TPBr)(tpy)](PF6)(2), and [Ru(TPBr)(2)](PF6)(2), synthesized by selective metalation of the NCNBr-pincer moiety or complexation of the terpyridine of the bifunctional ligand TPBr, were used as building blocks for the preparation of heterodi- and trimetallic complexes [Ru(TPPdCl)(tpy)](PF6)(2) (7) and [Ru(TPPdCl)(2)]-(PF6)(2) (8). The molecular structures in the solid state of [PdBr(TP)] (4a) and [Ru(TPBr)(2)](PF6)(2) (6) have been determined by single-crystal X-ray analysis. Electrochemical behavior and photophysical properties of the mono-and heterometallic complexes are described. All the above di- and trimetallic Ru complexes exhibit absorption bands attributable to (MLCT)-M-1 (Ru -> tpy) transitions. For the heteroleptic complexes, the transitions involving the unsubstituted tpy ligand are at a lower energy than the tpy moiety of the TPBr ligand. The absorption bands observed in the electronic spectra for TPBr and [PdCl(TP)] have been assigned with the aid of TD-DFT calculations. All complexes display weak emission both at room temperature and in a butyronitrile glass at 77 K. The considerable red shift of the emission maxima relative to the signal of the reference compound [Ru(tpy)(2)](2+) indicates stabilization of the luminescent (MLCT)-M-3 state. For the mono- and heterometallic complexes, electrochemical and spectroscopic studies (electronic absorption and emission spectra and luminescence lifetimes recorded at room temperature and 77 K in nitrile solvents), together with the information gained from IR spectroelectrochemical studies of the dimetallic complex [Ru(TPPdSCN)(tpy)](PF6)(2), are indicative of charge redistribution through the bridging ligand TPBr. The results are in line with a weak coupling between the {Ru(tpy)(2)} chromophoric unit and the (non)metalated NCN-pincer moiety.

Dimorphosim of a dimethoxy bridged oxovanadium(v)-hydrazone complex

A monoclinic variety with C2/c space group of the title complex [(VO)-O-V(L)(OCH3)](2), incorporating the doubly deprotonated benzoyl hydrazone of 2-hydroxy-5-methylacetophenone (H2L) was synthesized from the decomposition of [(VO)-O-IV(L)(bipy)] (where bipy representing the 2,2'-bipyridine) in methanol which has been reported very recently from our laboratory In this paper we report another monoclinic variety of this complex with P2(1)/n space group that showed some differences in bonding patterns in the solid state (but in solution they are almost identical) prepared by different synthetic method viz, from the equimolar reaction of [(VO)-O-IV(acac)(2)], H2L and imidazole in CH3OH.

Synthesis of new phosphino amino alcohol ligands via ortho-alkyllithiation reactions. Versatile coordination behavior toward copper(I) and palladium(II)

2-[Methyl(2-methylphenyl)amino]ethanol undergoes an ortho-alkyllithiation reaction with n-butyllithium to lead to a new mixed benzyllithium−lithium alkoxide. This organolithium species reacts with PPh2Cl, with selective P−C bond formation, to afford the ligand 2-[methyl(2-((diphenylphosphino)methyl)phenyl)amino]ethanol L1. The coordination of the ligand L1 to copper(I) leads to the complex [Cu(L1)2](BF4), whose structure has been determined by an X-ray diffraction study. In the solid state, one of the ligands acts as a monodentate phosphine while the other adopts a tridentate P,N,O coordination mode. A variable-temperature 31P NMR study demonstrated the existence of an equilibrium between the two modes in solution, with a coalescence temperature of ca. 0 °C, indicating a double-hemilabile behavior for the nitrogen and the oxygen functions. L1 reacts with [Pd(Me)(Cl)(COD)] to give a dinuclear complex in which the ligand appears to behave as a bridging anionic P,O ligand. Such a complex could serve as a model for a key intermediate in the proposed mechanism for the homogeneous catalysis of the methoxycarbonylation of propyne by certain palladium(II) complexes containing P,N ligands. L1 can undergo a second ortho-alkylmetalation reaction with n-butyllithium which, after addition of PPh2Cl, provides the new ligand 2-{methyl[2-(bis(diphenylphosphino)methyl)phenyl]amino}ethanol (L2) in high yield.

Synthesis, structure and electrochemical properties of some thiosemicarbazone complexes of ruthenium

Reaction of salicylaldehyde thiosemicarbazone (L-1), 2-hydroxyacetophenone thiosemicarbazone (L-2) and 2-hydroxynapthaldehyde thiosemicarbazone (L-3) with [Ru(dmso)(4)Cl-2] affords a family of three dimeric complexes (1), (2) and (3) respectively. Crystal structure of the complex (3) has been determined. In these complexes, each monomeric unit consists of one ruthenium center and two thiosemicarbazone ligands, one of which is coordinated to ruthenium as O,N,S-donor and the other as N,S-donor forming a five-membered chelate ring. Two such monomeric units remain bridged by the sulfur atoms of the O,N,S-coordinated thiosemicarbazones. Due to this sulfur bridging, the two ruthenium centers become so close to each other, that a ruthenium-ruthenium single bond is also formed. All the complexes are diamagnetic in the solid state and in dimethylsulfoxide solution show intense absorptions in the visible and ultraviolet region. Origin of these spectral transitions has been established from DFT calculations. Cyclic voltammetry on the complexes shows two irreversible ligand oxidations on the positive side of SCE and two irreversible ligand reductions on the negative side.

Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: a new one-dimensional indium selenide

A new organically templated indium selenide, [C6H16N2][In2Se3(Se2)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV–vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C6H16N2][In2Se3(Se2)] contains anionic chains of stoichiometry [In2Se3(Se2)]2−, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In2Se3(Se2)]2− chains, which consist of alternating four-membered [In2Se2] and five-membered [In2Se3] rings, contain perselenide (Se2)2− units. UV–vis diffuse reflectance spectroscopy indicates that [C6H16N2][In2Se3(Se2)] has a band gap of 2.23(1) eV

Salt and ionic cocrystalline forms of amides: protonation of carbamazepine in aqueous media

The products of reactions of the pharmaceutical amide carbamazepine (CBZ) with strong acids under aqueous conditions were investigated by both powder and single crystal X-ray diffraction. Despite previous claims to the contrary, it was found that salt forms with CBZ protonated at the amide O atom could be isolated from reactions with both HCl and HBr. These forms include the newly identified hydrate phase [CBZ(H)][Cl]·H O. Reactions with other mineral acids (HI and HBF ) gave ionic cocrystalline (ICC) forms (CBZ· [acridinium][I ]·2.5I and CBZ·[H O ] [BF ] ·H O) as well as the salt form CBZ·[CBZ(H)][BF ]·0.5H O. Reaction 2 4 3 2 5 2 0.25 4 0.25 2 4 2 of CBZ with a series of sulfonic acids also gave salt forms, namely, [CBZ(H)][O SC H ], [CBZ(H)][O SC H (OH)]· 3 6 5 3 6 4 0.5H O, [CBZ(H)] [O SCH CH SO ], and [CBZ(H)][O SC H (OH) (COOH)]·H O. CBZ and protonated CBZ(H) 2 2 3 2 2 3 3 6 3 2 moieties can be differentiated in the solid state both by changes to molecular geometry and by differing packing preferences