Thermodynamics of metal-ligand bond formation. XIV. Adducts of hetercyclic bases with nickel(II) alkylxanthates

1974 ◽  
Vol 27 (10) ◽  
pp. 2099 ◽  
Author(s):  
DP Graddon ◽  
S Prakash
Keyword(s):  
Free Energy ◽  
Alkyl Group ◽  
Benzene Solution ◽  
Bond Formation ◽  
Adduct Formation ◽  
Steric Effects ◽  
Alkyl Chains ◽  
Inductive Effects ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data have been obtained for the formation in benzene solution of adducts of nickel(11) O-alkylxanthate complexes with one molecule of 2,2'-bipyridine or two molecules of pyridine or 4-methylpyridine. The results show that changes in the free energy and enthalpy of adduct formation with variation of the alkyl group in the xanthate can be explained wholly by inductive effects; there is no evidence for steric effects even with branched alkyl chains.

Thermodynamics of metal-ligand bond formation. II. Zinc, cadmium, and mercury(II) complexes of o,o-dialkyldithiophosphates

1971 ◽  
Vol 24 (10) ◽  
pp. 2077 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Metal Atom ◽  
Alkyl Group ◽  
Thermodynamic Data ◽  
Benzene Solution ◽  
Bond Formation ◽  
Free Energies ◽  
Zinc Cadmium ◽  
Metal Ligand ◽  
Ligand Bond

The reactions of 0,O-dialkyldithiophosphato complexes, {(R0)2PSz}zM (M = Zn, Cd, Hg), to form dimers and 1 : 1 and 1 : 2 adducts with pyridine have been studied calorimetrically in benzene solution a t 30�C. While variation of the alkyl group has little effect, variation of the metal atom causes marked changes in both free energies and enthalpies of reaction. Average values of thermodynamic data obtained are as follows (AGOao3 and AH0300 in k J mol-l, AS0a03 in J K-l mol-l) :

scholarly journals Thermodynamics of metal-ligand bond formation. VIII. Pyridine adducts of zinc(II) β-diketonates

1973 ◽  
Vol 26 (11) ◽  
pp. 2537 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Benzene Solution ◽  
Equilibrium Constants ◽  
Bond Formation ◽  
Formation Constants ◽  
Adduct Formation ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Experimental Conditions ◽  
Metal Ligand ◽  
Ligand Bond

Equilibrium constants and enthalpies in benzene solution are reported for the formation of 1 : 1-adducts of pyridine with four zinc(II) complexes of β-diketones, determined by calorimetric titration. Adduct formation constants at 30�C fall in the range 300-2000 and enthalpies of formation lie between -15 and - 34 kJ mol-1. Though the enthalpies of formation differ little from those of corresponding copper(II) complexes, the adducts are about a hundred times more stable. The pyridine adduct of bis(2,2,6,6-tetramethylheptane-3,5-dionato)zinc(II) is entropy-stabilized relative to those of other complexes. No evidence was obtained for the addition of a second molecule of pyridine under the experimental conditions used.

Thermodynamics of metal-ligand bond formation. XXIV. Reaction of mercury(II) halides with tertiary arsines and phosphine and arsine sulphides

1976 ◽  
Vol 29 (11) ◽  
pp. 2409 ◽  
Author(s):  
MJ Gallagher ◽  
DP Graddon ◽  
AR Sheikh
Keyword(s):  
Thermodynamic Data ◽  
Benzene Solution ◽  
Bond Formation ◽  
Adduct Formation ◽  
Dilute Solution ◽  
Calorimetric Titration ◽  
Factors Affecting ◽  
Tertiary Arsines ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data have been obtained by calorimetric titration for the formation of 1 : 1 adducts of mercury(11) halides with tertiary arsines in benzene solution. In contrast to phosphines, only one molecule of arsine adds to HgX2 in dilute solution. Enthalpies of adduct formation, in the range - ΔH� = 50-80 kJ mol-1, are not much changed by replacement of phenyl by methyl, but adduct stabilities increase in the order Ph3As < Ph2AsMe < PhAsMe2 < AsMe3 HgI2AsMe3 is dimeric in solution. The diarsines Ph2As(CH2),AsPh2 are unidentate, but Ph2P- (CH2),AsPh2 is bidentate. Data are also reported for addition to HgX2 of Ph3PS,Ph2PSCH2PSPh2 and corresponding arsine sulphides; the disulphides are bidentate. Factors affecting chelation in these compounds are discussed.

Thermodynamics of metal-ligand bond formation. VI. Trimerization and base addition of nickel(II) β-diketonates

1973 ◽  
Vol 26 (9) ◽  
pp. 1901 ◽  
Author(s):  
LT Ang ◽  
DP Graddon
Keyword(s):  
Enthalpy Of Formation ◽  
Benzene Solution ◽  
Bond Formation ◽  
Steric Effects ◽  
Calorimetric Titration ◽  
Relative Stabilities ◽  
The Enthalpy Of Formation ◽  
Metal Ligand ◽  
Ligand Bond

Five nickel(II) complexes of β-diketones (LH) have been studied by calorimetric titration with pyridine in benzene solution. Trimerization of the complexes NiL2 is endothermic and entropy-driven, probably as a result of desolvation of the low-spin monomers. Reaction with pyridine occurs in two steps, forming successively Ni2L4(py) and NiL2(py)2. The enthalpy of formation of NiL2(py)2 from the intermediate adduct is about -40 kJ mol-1 and shows no evidence for bulkiness of the ligand leading to steric instability in Ni2L4(py). Variations in the relative stabilities of the monomeric and trimeric forms of NiL2 seem more likely to be due to electronic than steric effects.

Thermodynamics of metal-ligand bond formation. XXII. Zinc(II) and cadmium(II) dialkyldithiocarbamates

1976 ◽  
Vol 29 (7) ◽  
pp. 1429 ◽  
Author(s):  
L Ang ◽  
DP Graddon
Keyword(s):  
Thermodynamic Data ◽  
Benzene Solution ◽  
Bond Formation ◽  
Adduct Formation ◽  
Heterocyclic Bases ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data are reported for dimerization of dialkyldithiocarbamates, (R2NCS2)2Cd, and for addition of heterocyclic bases to (R2NCS2)2Cd and (R2NCS2)2Zn in benzene solution. Enthalpies of reaction are comparable to those of corresponding dithiophosphates, but adduct formation and dimerization constants are smaller and the dithiocarbamates add only one molecule of base. Though probably bidentate, 2,2'-bipyridine forms less stable adducts with (R2NCS2)2Zn than does pyridine.

Thermodynamics of metal-ligand bond formation. XV. Adducts of mercury(II) halides with bidentate bases

1974 ◽  
Vol 27 (10) ◽  
pp. 2103 ◽  
Author(s):  
Y Farhangi ◽  
DP Graddon
Keyword(s):  
Thermodynamic Data ◽  
Benzene Solution ◽  
Bond Formation ◽  
Adduct Formation ◽  
Mercury Atom ◽  
Satisfactory Explanation ◽  
Metal Ligand ◽  
Enthalpy Data ◽  
Ligand Bond

Thermodynamic data are reported for the reaction of mercury(11) halides with a range of potentially bidentate bases in benzene solution. The enthalpy data show that in 1 : 1 adducts with tetramethyl-alkanediamines and bis(diphenylphosphino)ethane both donor atoms are coordinated, the mercury being four-coordinate with two Hg-N or Hg-P bonds, each of comparable strength to those in 1 : 1 adducts with unidentate bases. N-Methylmorpholine and dioxan are almost certainly unidentate. 1,10-Phenanthroline, 2,2'-bipyridine and N,N'-dimethylpiperazine gave 1 : 1 adducts of higher stability than those of unidentate bases, but the enthalpies of adduct formation were similar or smaller; the most satisfactory explanation of this seems to be that both nitrogen atoms arecoordinated but that the two Hg-N bonds are unusually weak because of steric misfitting of the bidentate base with the mercury atom.

Thermodynamics of metal-ligand bond formation. III. Adducts of heterocyclic bases with Bis(N-nitroso-N-phenylhydroxylaminato)copper(II)

1971 ◽  
Vol 24 (11) ◽  
pp. 2267 ◽  
Author(s):  
DP Graddon ◽  
CY Hsu
Keyword(s):  
Steric Hindrance ◽  
Benzene Solution ◽  
Bond Formation ◽  
Adduct Formation ◽  
Thermometric Titration ◽  
Sterically Hindered ◽  
Heterocyclic Bases ◽  
Metal Ligand ◽  
Ligand Bond

The copper(II) complex of N-nitroso-N-phenylhydroxylamine (copper cupferrate) reacts with heterocyclic bases in benzene solution to form 1 : 1-adducts. Enthalpies and entropies of adduct formation with a range of bases have been determined by thermometric titration. The results, which are similar to those obtained with copper(II) complexes of β-diketones, reveal two isoequilibrium series for sterically hindered and unhindered bases, and indicate that the effect of the steric hindrance is probably to restrict rotation of the base molecule about the newly formed metal-ligand bond.

Thermodynamics of metal-ligand bond formation. XX. Reaction of tertiary phosphines with mercury(II) halides

1976 ◽  
Vol 29 (4) ◽  
pp. 759 ◽  
Author(s):  
MJ Gallagher ◽  
DP Graddon ◽  
AR Sheikh
Keyword(s):  
Linear Relationship ◽  
Benzene Solution ◽  
Bond Formation ◽  
Enthalpies Of Formation ◽  
Bridging Ligand ◽  
Tertiary Phosphines ◽  
Inductive Effects ◽  
Metal Ligand ◽  
Enthalpy Data ◽  
Ligand Bond

Tertiary phosphines form highly stable 1 : 1 and 2 : 1 adducts with mercury(11) halides in benzene solution. In the series of phosphines (alkyl),PPh3-n enthalpies of formation are determined by inductive effects and give a linear relationship with Taft constants, ∑σ*. The cyclic phosphine 1,2,5-triphenylphosphole is a much weaker base towards the mercury(11) halides. While ethane-1,2- diylbis(dipheny1phosphine) behaves only as a chelate, methylenebis(dipheny1phosphine) can behave both as a chelate and as a bridging ligand and propane-1,3-diylbis(dipheny1phosphine) only as a bridging ligand. The unsaturated diphosphines (2)- and (E)-ethene-l,2-diylbis(dipheny1phosphine) both form 1 : 1 adducts with mercury(11) halides in benzene solution in which the phosphines are unidentate. Enthalpy data are reported for the formation of all these adducts.

Thermodynamics of metal-ligand bond formation. XII. Adducts of Monothio-β-diketone complexes with pyridine and bipyridine

1974 ◽  
Vol 27 (6) ◽  
pp. 1351 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Thermodynamic Data ◽  
Benzene Solution ◽  
Bond Formation ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data are reported for the addition of pyridine and bipyridine in benzene solution to monothio-β-diketone complexes, ML2, of nickel(11), copper(11), zinc(11) and mercury(11). NiL2 gives NiL2(py)2 and NiL(bpy); ZnL2 gives ZnL2(py) and ZnL2(bpy); in both cases the data show that bipyridine is bidentate. CuL2 gives CuL2 (py) and CuL2 (bpy), with almost equal enthalpies of formation, but the higher stability of CuL2(bpy) shows bipyridine is probably bidentate. HgL2 gives HgL2(py) and a reaction with bipyridine which shows that an extremely unstable adduct is formed. All data were obtained by calorimetric titration.

Thermodynamics of metal-ligand bond formation. XXV. Addition of bases to Bis[O,O'-diethyl thiomalonato]nickel(II) in various solvents

1977 ◽  
Vol 30 (3) ◽  
pp. 495 ◽  
Author(s):  
L Ang ◽  
DP Graddon ◽  
VAK Ng
Keyword(s):  
Thermodynamic Data ◽  
Driving Force ◽  
Bond Formation ◽  
Adduct Formation ◽  
Calorimetric Measurements ◽  
Carbon Tetra ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data have been obtained from spectroscopic and calorimetric measurements for the addition of pyridine and 4- methylpyridine to bis(O,O?-diethyl thiomalonato)nickel(II), Ni(etm)2, in solution in cyclohexane, benzene, 1,2-dichloroethane, acetonitrile, butan-2-one and carbon tetra-chloride. In each solvent two base molecules add successively, giving Ni(etm)2B then Ni(etm)2B2. There are only small variations in K1 and K2 in different solvents; typically K1 ≈ 200, K2 ≈ 100 l. mol-1, ΔH�1+2 ≈ -65, ΔH�2 ≈ 0 kJ mol-1 at 30�C, but in benzene and cyclohexane ΔH�2 ≈ -25 and in cyclohexane ΔH�1+2 ≈ -100 kJ mol-1. The main driving force for adduct formation is apparently the formation of the first Ni-N bond, which is accompanied by a spin change.

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