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1.
Massimo Di Vaira Fabrizio Mani Piero Stoppioni 《Journal of organometallic chemistry》2004,689(10):1757-1762
The reaction of [CpRu(CH3CN)3]PF6 with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η2-L-L)(CH3CN)]PF6, [{CpRu(CH3CN)2}2(μ-η1:1-L-L)](PF6)2 and [{CpRu(CH3CN)}2(μ-η1:1-L-L)2](PF6)2 (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [1H and 31P{1H}] spectroscopy. The crystal structure of [{CpRu(CH3CN)2}2(μ-η1:1-dppe)](PF6)2 has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH3CN)2 fragments. 相似文献
2.
Ford S Hofmann M Morley CP Roberts JL Di Vaira M 《Organic & biomolecular chemistry》2005,3(21):3990-3995
Bis(1,2,3,4-tetramethylcyclopentadienyl)selane (1) has been prepared by the reaction of tetramethylcyclopentadienyllithium (Cp(t)Li) with selenium bis(diethyldithiocarbamate). Treatment of Cp(t)Li with elemental selenium, followed by air oxidation, led to loss of the allylic hydrogen atom, and formation of the novel tricyclic compound 1,4,5,6,7,10,11,12-octamethyltricyclo[7.3.0.0]-2,8-diselenadodeca-3,5,9,11-tetraene (2). The sulfur analogue of 2 has been obtained by a similar procedure. The X-ray crystal structures of compounds 1 and 2 have been determined, and the molecular geometry observed for has been probed using DFT calculations. 相似文献
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4.
This short review describes a breakthrough provided by the synthesis of d6 metal complexes containing the intact molecules P4 and P4S3. The coordinated cage molecules acquire unexpected reactivity and undergo dismutation reactions in mild conditions in the presence of water. The outcomings are obtained either in form of free or coordinated molecules; the former are hypophosphorous and phosphorous acids, the latter comprise, besides phosphine, PH3, such species as thiophosphinous acid, PH2SH, diphosphane, P2H4, 1-hydroxytriphosphane, PH(OH)PHPH2 and 1,1,4-tris-hydroxytetraphosphane, P(OH)2PHPHPH(OH), which are either unknown or extremely reactive as free molecules. The formation of the above molecules provides a clue to the hydrolytic activation of the P4 and P4S3 cage molecules. 相似文献
5.
Akbayeva DN Di Vaira M Costantini SS Peruzzini M Stoppioni P 《Dalton transactions (Cambridge, England : 2003)》2006,(2):389-395
Treatment of [CpRu(PPh(3))(2)Cl] 1 with the stoichiometric amount of H(3)PO(2) or H(3)PO(3) in the presence of chloride scavengers (AgCF(3)SO(3) or TlPF(6)) yields compounds of formula [CpRu(PPh(3))(2)(HP(OH)(2))]Y (Y = CF(3)SO(3) 2a or PF(6) 2b) and [CpRu(PPh(3))(2)(P(OH)(3))]Y (Y = CF(3)SO(3) 3aor PF(6) 3b) which contain, respectively, the HP(OH)(2) and P(OH)(3) tautomers of hypophosphorous and phosphorous acids bound to ruthenium through the phosphorus atom. The triflate derivatives 2a and 3a react further with hypophosphorous or phosphorous acids to yield, respectively, the complexes [CpRu(PPh(3))(HP(OH)(2))(2)]CF(3)SO(3) 4 and [CpRu(PPh(3))(P(OH)(3))(2)]CF(3)SO(3) 5 which are formed by substitution of one molecule of the acid for a coordinated triphenylphosphine molecule. The compounds 2 and 3 are quite stable in the solid state and in solutions of common organic solvents, but the hexafluorophosphate derivatives undergo easy transformations in CH(2)Cl(2): the hypophosphorous acid complex 2b yields the compound [CpRu(PPh(3))(2)(HP(OH)(2))]PF(2)O(2) 6, whose difluorophosphate anion originates from hydrolysis of PF(6)(-); the phosphorous acid complex 3b yields the compound [CpRu(PPh(3))(2)(PF(OH)(2))]PF(2)O(2) 7, which is produced by hydrolysis of hexafluorophosphate and substitution of a fluorine for an OH group of the coordinated acid molecule. All the compounds have been characterized by elemental analyses and NMR measurements. The crystal structures of 2a, 3a and 7 have been determined by X-ray diffraction methods. 相似文献
6.
In this paper we study the Schrödinger-Poisson system
(SP) 相似文献
7.
Francesco Tavella Daniele Giusi Claudio Ampelli 《Current Opinion in Green and Sustainable Chemistry》2022
The direct electrocatalytic production of ammonia (NH3) from N2 and H2O at ambient conditions is one of today's chemical challenges to meet the growing industrial demand for ammonia. Despite numerous studies on designing novel catalysts to activate N2 molecule and elucidating the reaction mechanism, many critical factors (such as gas diffusion and charge transfer limitations that instead promote the side reaction of hydrogen evolution) remain unsolved, suggesting that a breakthrough is needed to improve performance in this challenging reaction. Based on this, we review here recent studies that propose advanced solutions, focusing on: (i) the adoption of a three-dimensional nanoarchitecture of the electrode surface (to favour multi-electron transfer), (ii) the design of cell configuration (including the development of gas diffusion electrodes – GDEs), (iii) the critical aspects of the more efficient lithium-mediated approach in non-aqueous solvents (flooding of the GDE, sustainability of the proton-shuttle system), (iv) new methods for ammonia detection avoiding false positive. 相似文献
8.
Massimo Di Vaira Stefano Seniori Costantini 《Journal of organometallic chemistry》2006,691(18):3931-3937
The reaction of [CpRu(dppe)Cl] (1), dppe = 1,2-bis(diphenylphosphino)ethane, with one equivalent of P4 in the presence of TlPF6 affords the stable complex [CpRu(dppe)(η1-P4)]PF6 (2) which contains the tetrahedral P4 molecule η1-bound to the metal. The tetraphosphorus ligand readily reacts with water upon mixing acetone or THF solutions of the complex with excess water. The complexes [CpRu(dppe)(PH3)]PF6 (5) and [CpRu(dppe){P(OH)3}]PF6 (6), identified among the hydrolysis products, contain the PH3 molecule and, respectively, the unstable P(OH)3 tautomer of the phosphorous acid bound to the CpRu(dppe) fragment. In CH2Cl2 the coordinated P(OH)3 molecule in 6 easily yields the compound [CpRu(dppe){PF(OH)2}]PF2O2 (8), via hydrolysis of the hexafluorophosphate anion and F/OH substitution in the coordinated P(OH)3 molecule. All the compounds have been characterized by elemental analyses and NMR measurements. The crystal structures of 2 and 8 have been determined by X-ray diffraction methods. 相似文献
9.
Jing S Morley CP Webster CA Di Vaira M 《Dalton transactions (Cambridge, England : 2003)》2006,(36):4335-4342
Reaction of a 1,3-bis(ferrocenylchalcogeno)propane, FcE(CH2)3E'Fc (L: E, E' = Se or Te; Fc = [Fe(eta5-C5H5)(eta5-C5H4)]), with a palladium(II) or platinum(II) precursor [M(NCMe)4](PF6)2 (M = Pd or Pt) in acetonitrile at room temperature led in good yield to the bis-chelate complexes [ML2](PF6)2. The structures of FcSe(CH2)3SeFc and all six complexes have been determined by X-ray crystallography. Electrochemical studies showed that electronic communication between ferrocenyl groups, absent in all three bis(ferrocenylchalcogeno)propanes, is established on complexation only for E = Se and E' = Se or Te, when the through-bond Fe...Fe distance is reduced to 13.17 A or less. 相似文献
10.
Di Vaira M Bazzicalupi C Orioli P Messori L Bruni B Zatta P 《Inorganic chemistry》2004,43(13):3795-3797
Clioquinol, a 8-hydroxyquinoline derivative, is producing very encouraging results in the treatment of Alzheimer's disease (AD). Its biological effects are most likely ascribed to complexation of specific metal ions, such as copper(II) and zinc(II), critically associated with protein aggregation and degeneration processes in the brain. We report here, for the first time, a structural characterization of the zinc(II) and copper(II) complexes of clioquinol. A ligand to metal stoichiometry of 2:1 is found in both cases, though in the presence of quite different coordination polyhedra. The present findings are discussed in the frame of modern approaches to AD treatment. 相似文献