Thermodynamics of metal-ligand bond formation

Farhangi, Y.; Graddon, DP

doi:10.1016/s0022-328x(00)80344-7

Cited by 47 publications

(15 citation statements)

References 34 publications

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“…Similarly, no adducts of Ph3SnNCS (4) or Ph,SnNCSe (3) with a-picoline have been reported. While this may be due to steric hindrance by the a-methyl group, calorimetric titration studies (20) of the reactions of pyridine, a-picoline, and y-picoline with several organotin halides have shown the steric effect is due to an entropy factor rather than a change in the enthalpy of metal-ligand bond formation. Unlike its tin analogue, triphenyllead selenocyanate does not form adducts with pyridine, P-, or y-picoline, perhaps due to its weaker acceptor power.…”

Section: Resultsmentioning

confidence: 99%

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Adducts of triphenyllead isothiocyanate and selenocyanate with some O- and N-donor ligands

Wojtowski¹,

Wharf²,

Onyszchuk³

1983

Can. J. Chem.

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This paper is dedicatecl to Professor Leo Ycdfe or1 the occn.siorl of his 6.5111 birthdaj~ RYSZARD WOJTOWSKI, IVOR WHARF, and MARIO ONYSZCHUK. Can. J. Chcm. 61. 743 (1983).The preparation and properties of triphenyllead selenocyanate have been reinvestigated. Infrared spcctra show that the solid is polymeric with strong Pb-Se and weak Pb-N bonds; in benzene or CH2C12 solutions v(CN) values are consistent with the Ph,PbSeCN bonding mode. The first 1 : 1 adducts of triphenyllcad selenocyanatc with hexamethylphosphoramide (HMPA), pyridine-N-oxidc (pyO), 4-picoline-N-oxide (4-picO), and triphenylphosphinc oxide (TPPO) have been prepared; infrared data show that Ph,PbSeCN.L (L = pyO, 4-picO, TPPO) are selcnocyanates, but the HMPA adduct is an isoselenocyanate. The adducts dissociate in benzene and v(CN) frequencies show that both N-bonded and Se-bonded adduct isomers arc present. In contrast, thc adducts Ph3PbNCS.L (L = HMPA, pyO, 4-picO, TPPO) are N-bonded in the solid state and in benzenc solution where they are undissociated. Anline adducts, Ph3PbNCS.L (L = pyridine, P-picoline, y-picolinc, pyrrolidine (pyrrol), piperidine (pipy), cyclohexylamine (CyNH2)) and PhjPbNCS -2L (L = morpholine (morph)), as well as Ph3PbNCSe epipy and 2 Ph3PbNCSe.3L (L = pyrrol or morph) have been prepared. but thesc are less stable than adducts with 0-donor ligands. Infrared data suggest that amine adducts of Ph3PbNCS have N-bonded and/or ionic thiocyanate groups while all Ph3PbSeCN-amine adducts contain the sclenocyanate ion. [Traduit par le journal]

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Section: Resultsmentioning

confidence: 99%

“…This hypothesis is supported by the results of calorimetric studies by Graddon of the reaction R2SnC12 + L + R2SnC1,.L in benzene; e.g. for R = Ph, when L = pyO (22), AH = -39 kJ/mol, K = oc: (25"C), and when L = py (20), AH = -48 kJ/mol, K = 80…”

Section: Resultsmentioning

confidence: 99%

Adducts of triphenyllead isothiocyanate and selenocyanate with some O- and N-donor ligands

Wojtowski¹,

Wharf²,

Onyszchuk³

1983

Can. J. Chem.

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“…The IR spectral bands of complexes (1) and (2) at 588 and 633 cm -1, respectively are assigned to an antisymmetric Sn-C stretching mode [2,3]. The appearance of single Sn-C stretching band in both complexes (1) and (2), have shown that the two butyl groups are in trans positions in both complexes (1) and (2) [6]. Further, the cis-positions of the two chlorine atoms in both (1) and (2), have been confirmed by the appearance of Sn-C1 stretching bands for (1) at 210 and 225 cm -1, and for (2) at 232 and 263 cm -1 [2,3,6,11].…”

Section: Elemental Analyses Thermal Studies and Ir Spectral Datamentioning

confidence: 94%

“…The entropy AH change AS was calculated using the relation [10] AS = ~ where Tm is the DTA peak temperature in K. IR and far-IR spectra were recorded using Perkin Elmer 781 and 783 models in KBr and polythene discs, respectively. Compounds (1) and (2) had been reported earlier [6]. We have characterized the compounds by elemental analyses (Table 1) and IR spectra (Table 2).…”

Section: Elemental Analyses Thermal Studies and Ir Spectral Datamentioning

confidence: 99%

“…Although studies on organotin complexes are well known in literature [1][2][3][4][5][6], works on thermal investigation and stereochemical changes in the solid state are still very less. The main aim of our work is to synthesize some compounds of the type Me2SnCI2-2L and R2SnCIz.U, where L = pyridine, 4-picoline and L' =l,10-phenanthroline, 2,2'-bipyridyl and R =butyl, methyl group.…”

Section: Introductionmentioning

confidence: 99%

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Thermal investigation of some heterocyclic ligand complexes of tin(IV) in the solid state

Singh

Mitra

1991

Journal of Thermal Analysis

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1,10-phenanthroline (phen), 2,2'-bipyridyl (bipy), pyridine (py) and 4-picoline (4-pic) complexes of dibutyltindichloride (Bu2SnCI2) and dimethyltindichloride (Me2SnClz) were synthesized. The complexes were characterized with the help of elemental analyses, IR spectra and thermal analyses. The complexes were found to have the compositions 2(4-pic)]'H20. All these complex compounds appeared to posses octahedral structures. Thermodynamic parameters, such as activation energy E* enthalpy change AH and entropy change AS, for the dehydration and sublimation of the complexes were evaluated using some standard methods.

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σ‐Pyridine Coordination Compounds with Nontransition Metals

1985

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Thermodynamics of metal-ligand bond formation

Cited by 47 publications

References 34 publications

Adducts of triphenyllead isothiocyanate and selenocyanate with some O- and N-donor ligands

Adducts of triphenyllead isothiocyanate and selenocyanate with some O- and N-donor ligands

Thermal investigation of some heterocyclic ligand complexes of tin(IV) in the solid state

σ‐Pyridine Coordination Compounds with Nontransition Metals

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