Substitution reactions at the Ni(III) cation in macrobicyclic complexes – Reaction of metal ion complexes prepared from ligands L1 (17-oxa-1,4,8,11-tetraazabicyclo[6.5.6]nonadecane) and L2 (17-oxa-1,4,8,11-tetraazabicyclo[10.5.2]nonadecane) with chloride ion

2002 ◽  
Vol 80 (2) ◽  
pp. 155-162 ◽  
Author(s):  
Alison M Ingham ◽  
Chao Xu ◽  
T W Whitcombe ◽  
Chengtian Xu ◽  
J N Bridson ◽  
...  
Keyword(s):  
Metal Ion ◽  
Chloride Ion ◽  
Chemical Oxidation ◽  
Acid Dissociation ◽  
Acid Dissociation Constant ◽  
Substitution Reactions ◽  
Kinetic Measurements ◽  
Acidic Solutions ◽  
Square Planar ◽  
Ether Oxygen

The potentially penta-coordinating ligand L1 has been synthesized by reaction of the bridge bis-(2-(methylsulfonyl)oxyethyl)ether with the tetraazamacrocycle cyclam (cyclam = 1,4,8,11-tetraazatetradecane). The copper(II) complex was characterized initially and subsequent demetallation provided pure L1. Electrochemical and chemical oxidation of the nickel(II) species yields a Ni(III) ion (low-spin d7, rhombic, gxx 2.195, gyy 2.189, gzz 2.027) of sufficient stability in acidic solutions for kinetic measurements to be undertaken of substitution reactions at the sixth site. The isomeric ligand L2, has been synthesized previously, and reactions of the [Ni(L1)(solv)]3+ and [Ni(L2)(solv)]3+ ions with chloride have also been investigated. In both reactions, an unusually high acid dissociation constant is observed, associated with the proposed replacement of the apical ether oxygen by a water molecule that is bound both to the metal centre and hydrogen bonded to the ether. The structure [Ni(L2)](PF6)2 (monoclinic, P21/c, a = 10.699(2), b = 13.244(4), c = 16.603(2) Å, β = 92.10(1)°) converged at R = 0.055 (R' = 0.057) for 325 parameters using 3293 reflections with I > 2σ(I). In this complex, the detachment of the ether O donor to yield a square-planar complex is confirmed. Comparisons are made with substitution rates at other Ni(III) macrocyclic ions.Key words: nickel(III), substitution, macrobicyclic ligand, synthesis, kinetics.

Carbodithioato derivatives of weak nitrogenous nucleophiles. I. Electronic structure and ground state properties of Ni(II) amide N-carbodithioates

1989 ◽  
Vol 67 (5) ◽  
pp. 902-909 ◽  
Author(s):  
C. C. Hadjikostas ◽  
G. A. Katsoulos ◽  
M. P. Sigalas ◽  
C. A. Tsipis
Keyword(s):  
Electronic Structure ◽  
Molecular Orbital ◽  
Metal Ion ◽  
Chemical Reactivity ◽  
Frontier Molecular Orbital ◽  
The Novel ◽  
Substitution Reactions ◽  
Square Planar ◽  
Elemental Analyses ◽  
Derivatives Of

Nickel(II) complexes of the general type [Ni(S2CN(COR′)R)2] have been synthesized by the reaction of the appropriate Ni(II) N-alkyldithiocarbamate with acetic anhydride or benzoyl chloride in the presence of triethylamine. The complexes obtained were identified and characterized by elemental analyses, conductivity measurements, and ir and electronic spectra. It was concluded that the bonding mode of the dithiocarbamato ligands to the metal ion is not altered by the acylation reaction, the chromophore remaining square-planar NiS4. Moreover, EHMO-SCCC calculations have been used in the analysis of electronic structure, and related properties of the novel compounds. From the calculated molecular orbital description of the complexes and the frontier molecular orbital approach of chemical reactivity, plausible mechanisms of their formation reactions have been deduced. Keywords: Ni(II) amide N-carbodithioates, N-alkyldithiocarbamates, dithiocarbimates, electrophilic substitution reactions, EHMO-SCCC calculations.

Structure of the complexes of ethylenediphosphinetetraacetic acid in solution

1985 ◽  
Vol 50 (2) ◽  
pp. 445-453 ◽  
Author(s):  
Jana Podlahová ◽  
Josef Šilha ◽  
Jaroslav Podlaha
Keyword(s):  
Metal Ion ◽  
Carboxyl Groups ◽  
Complex Solution ◽  
Square Planar ◽  
Weak Complexes ◽  
Carboxylic Groups ◽  
Uv Visible ◽  
The Stability ◽  
Tetrahedral Complexes ◽  
Free Carboxyl

Ethylenediphosphinetetraacetic acid is bonded to metal ions in aqueous solutions in four ways, depending on the type of metal ion: 1) through an ionic bond of the carboxylic groups to form weak complexes with a metal:ligand ratio of 1 : 1 (Ca(II), Mn(II), Zn(II), Pb(II), La(III)); 2) through type 1) bond with contributions from weak interaction with the phosphorus (Cd(II)); 3) through coordination of the ligand as a monodentate P-donor with the free carboxyl groups with formation of 2 : 1 and 1 : 1 complexes (Cu(I), Ag(I)); 4) through formation of square planar or, for Hg(II), tetrahedral complexes with a ratio of 1 : 2 with the ligand as a bidentate PP-donor with the free carboxyl groups (Fe(II), Co(II), Ni(II), Pd(II), Pt(II)). On acidification of the complex solution, the first two protons are bonded to the carboxyl groups. The behaviour during further protonation depends on the type of complex: in complexes of types 1) and 2) phosphorus is protonated and the complex dissociates; in complexes of types 3) and 4) the free carboxyl groups are protonated and the phosphorus-metal bond remains intact. The results are based on correlation of the stability constants, UV-visible, infrared, 1H and 31P NMR spectra and magnetic susceptibilities of the complexes in aqueous solution.

Accurate acid dissociation constant (pKa) calculation for the sulfachloropyridazine and similar molecules

2021 ◽  
Vol 27 (8) ◽  
Author(s):  
Fernando Marques Carvalho ◽  
Yuri Alves de Oliveira Só ◽  
Alessandra Sofia Kiametis Wernik ◽  
Mônica de Abreu Silva ◽  
Ricardo Gargano
Keyword(s):  
Dissociation Constant ◽  
Acid Dissociation ◽  
Acid Dissociation Constant ◽  
Pka Calculation

Dissociation of imino proton(s) of a highly water-soluble metal-free phthalocyanine and determination of its pKa value in water

2013 ◽  
Vol 17 (06n07) ◽  
pp. 447-453 ◽  
Author(s):  
Hiroaki Isago ◽  
Harumi Fujita
Keyword(s):  
Aqueous Media ◽  
Thermal Reaction ◽  
Water Soluble ◽  
Acid Dissociation ◽  
Acid Dissociation Constant ◽  
Metal Free ◽  
Imino Proton ◽  
Pka Value ◽  
Triton X

Dissociation of imino proton(s) in the cavity of the macrocycle of a highly water-soluble, metal-free phthalocyanine ( H 2( H 4 tsppc ); where H 4 tsppc denotes tetrakis{(2′,6′-dimethyl-4′-sulfonic acid)phenoxy}phthalocyaninate) in ethanolic and aqueous solutions has spectrophotometrically been investigated. The spectral changes associated with reaction with NaOH have been found to involve one-proton transfer process in aqueous media while two-protons process in ethanolic media. The acid-dissociation constant of the first imino proton in water (in the presence of Triton X-100) has been determined to be 12.5 ± 0.2 (as pKa) at 25 °C. The doubly deprotonated species in EtOH has been easily converted to its corresponding cobalt(II) derivative by thermal reaction with anhydrous CoCl 2.

Synthesis, characterisation and activity in catalytic epoxidation of olefins of new dinuclear nickel(ll) complexes

2009 ◽  
Vol 2009 (8) ◽  
pp. 527-532
Author(s):  
Manindranath Bera
Keyword(s):  
Visible Region ◽  
Chemical Oxidation ◽  
Cyclic Voltammetric ◽  
Catalytic Epoxidation ◽  
Redox Couples ◽  
Square Planar ◽  
Catalytically Active ◽  
Mecn Solution ◽  
Voltammetric Measurements ◽  
Epoxidation Of Olefins

Two new dinuclear nickel(ll) compounds of formula [Nill2(μ-L1)2](CIO4)2·MeCN (1·MeCN) and [NiII2(μ-L2)2](CIO4)2 (2) where HL1 and HL2 stand for 3-(2-(dimethylamino)ethylimino)butan-2-one oxime and 1-(2-(dimethylamino)ethyl-imino)-1-phenylpropan-2-one oxime respectively, have been synthesised. Single crystal X-ray analyses of the complexes reveal that the nickel(ll) ions are in square-planar N3O environments and form six-membered (NiNO)2 metallacycles. Cyclic voltammetric measurements of 1·MeCN and 2 in MeCN solution show quasirreversible one-electron oxidations at E1/2 = 0.566 V and 0.603 V ( vs Fc+/Fc), respectively, attributed to NiIIINiII/NiII2 redox couples. Additional reversible NiIII2/NiIIINiII redox responses were observed at relatively higher potential near E1/2 = 0.832 V and 0.850 V ( vs Fc+/Fc), respectively, for 1·MeCN and 2. Complexes 1·MeCN and 2 display intense charge-transfer bands at ∼390 and ∼345 nm in the visible region. Chemical oxidation of complex 1·MeCN by sodium hexachloroiridate(IV) hexahydrate generates red Ni2III species with characteristic new bands at ∼520 and 427 nm in the visible region as well as the characteristic EPR signals at 77 K with g⊥ > gII. Similar phenomena were observed for complex 2 upon chemical oxidation. The dinickel(ll) complexes are catalytically active for epoxidation of olefins using iodosylbenzene as the terminal oxidant.

scholarly journals Investigations of ternary complexes of Co(II) and Ni(II) with thiodiacetate anion and 1,10-phenanthroline or 2,2’-bipyridine in aqueous solutions

2014 ◽  
Vol 13 (1) ◽  
Author(s):  
Dariusz Wyrzykowski ◽  
Joanna Pranczk ◽  
Dagmara Jacewicz ◽  
Aleksandra Tesmar ◽  
Bogusław Pilarski ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Substitution Reactions ◽  
Experimental Conditions ◽  
Kinetic Measurements ◽  
Hydroxo Complexes ◽  
Binary Complexes ◽  
Vis Spectroscopy ◽  
Potentiometric Titration Method ◽  
The Stability ◽  
Ph Range

AbstractA potentiometric titration method (PT) and a stopped-flow kinetic technique monitored by a UV−Vis spectroscopy have been used to characterize the stability of series of Co(II)- and Ni(II)-thiodiacetato complexes, M(TDA), in the presence of 1,10-phenanthroline (phen) or 2,2’-bipyridine (bipy) in aqueous solutions. The stability constants of the binary (1:1), ternary (1:1:1) as well as the resulting hydroxo complexes were evaluated and compared to the corresponding oxydiacetate complexes. Based on the species distribution as a function of pH the relative predominance of the species in the system over a pH range was discussed. Furthermore, the kinetic measurements of the substitution reactions of the aqua ligands to phen or bipy in the coordination sphere of the binary complexes M(TDA) were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (0.2–0.5 mM). The kinetic stability of the M(TDA) complexes was discussed in relation to the experimental conditions and the kind of the auxiliary ligands (phen/bipy). Moreover, the influence of the type of primary ligand (thiodiacetate/oxydiacetate) on the substitution rate of the auxiliary ligands was also compared.

scholarly journals Crystal structures of [Mn(bdc)(Hspar)2(H2O)0.25]·2H2O containing MnO6+1capped trigonal prisms and [Cu(Hspar)2](bdc)·2H2O containing CuO4squares (Hspar = sparfloxacin and bdc = benzene-1,4-dicarboxylate)

2016 ◽  
Vol 72 (1) ◽  
pp. 96-101
Author(s):  
Zhe An ◽  
Jing Gao ◽  
William T. A. Harrison
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Crystal Structures ◽  
Metal Ion ◽  
Three Dimensional ◽  
Trigonal Prism ◽  
Planar Geometry ◽  
Cationic Complex ◽  
Counter Ion ◽  
Square Planar

The syntheses and crystal structures of 0.25-aqua(benzene-1,4-dicarboxylato-κ2O,O′)bis(sparfloxacin-κ2O,O′)manganese(II) dihydrate, [Mn(C8H4O4)(C19H22F2N4O3)2(H2O)0.25]·2H2O or [Mn(bdc)(Hspar)2(H2O)0.25]·2H2O, (I), and bis(sparfloxacin-κ2O,O′)copper(II) benzene-1,4-dicarboxylate dihydrate, [Cu(C19H22F2N4O3)2](C8H4O4)·2H2O or [Cu(Hspar)2](bdc)·2H2O, (II), are reported (Hspar = sparfloxacin and bdc = benzene-1,4-dicarboxylate). The Mn2+ion in (I) is coordinated by twoO,O′-bidentate Hspar neutral molecules (which exist as zwitterions) and anO,O′-bidentate bdc dianion to generate a distorted MnO6trigonal prism. A very long bond [2.580 (12) Å] from the Mn2+ion to a 0.25-occupied water molecule projects through a square face of the prism. In (II), the Cu2+ion lies on a crystallographic inversion centre and a CuO4square-planar geometry arises from its coordination by twoO,O′-bidentate Hspar molecules. The bdc dianion acts as a counter-ion to the cationic complex and does not bond to the metal ion. The Hspar ligands in both (I) and (II) feature intramolecular N—H...O hydrogen bonds, which closeS(6) rings. In the crystals of both (I) and (II), the components are linked by N—H...O, O—H...O and C—H...O hydrogen bonds, generating three-dimensional networks.

Novel Inorganic Hydrogels Based on The Polymerization of Cyanometalate Transition Metal Complexes With [PdCl4]2-: A New Approach To Ceramic And Alloy Precursors

1994 ◽  
Vol 346 ◽  
Author(s):  
Andrew B. Bocarsly ◽  
Gireesh Kumar ◽  
Marija Heibel
Keyword(s):  
Transition Metal ◽  
Metal Ion ◽  
Sol Gel ◽  
Metallic Matrix ◽  
Linear Polymers ◽  
New Approach ◽  
Square Planar ◽  
Delafossite Structure ◽  
Cyanide Ligand ◽  
Sol Gel Transition

ABSTRACTThe reaction of a wide variety of cyanometalate complexes of the general form [M(CN)x]n- (where M= a transition metal ion) with square planar [PdCl4]2- in aqueous solution leads to the formation of linear polymers. Polymerization occurs via substitution of chloride ligands on the Pd(II) centers, by the nitrogen end of the cyanide ligand to generate extended bridging cyanide structures. Upon generation at room temperature polymer solutions of this type under go a sol-gel transition to generate robust hydrogels having water content in excess of 95%. In the case of the cyanocobaltate/tetrachloropalladate gel, pyrolysis at 900°C produces ferromagnetic Pd/Co metallic alloys having novel morphological character. Materials formed with a hydrogel having a 2:1 Pd to Co stoichiometry are found to be “sponge-like”. When placed in water, the metallic matrix swells becoming pliable and holding up to seven equivalents of water per metal site. The conductivity and magnetic properties of this material are maintained in the swollen state. Sintering of the Pd/Co hydrogel in air generates the layered oxide, PbCoO2 having a delafossite structure.

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