Thermochemistry of dichlorobis(triphenylphosphine oxide)-zinc(II), -cadmium(II), and -mercury(II)

Jorge, Renato Atílio; Airoldi, Cláudio; Chagas, Aécio P.

doi:10.1039/dt9780001102

Cited by 31 publications

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“…such a way, it was assumed that the enthalpy of 1 mol of ligand is equal to the enthalpy of sublimation of the adduct (26). It is clearly known from infrared spectra that the metal is bound to oxygen, so AHge/n = AH(,-,,@ and its value is higher for monoadducts, as was observed previously.…”

Section: Resultsmentioning

confidence: 60%

“…Under the conditions of the physical measurements such as melting point, thermogravimetry, and mass spectrometry one knows that the adducts decompose during the heating and the enthalpy of sublimation of the adduct is not accessible experimentally (26). In this case, the enthalpy of metalligand bond can be estimated (7,8,26).…”

Section: Resultsmentioning

confidence: 99%

“…Both thermochemical parameters have been used to compare and systematize adducts which do not sublime without decomposition (7,8,26,27). The enthalpy of formation of the adducts also presents the same trend in variation.…”

Section: Resultsmentioning

confidence: 99%

“…In this case, the enthalpy of metalligand bond can be estimated (7,8,26). For that evaluation the enthalpy of reaction in the gas phase: MX2(g) + nmu(g) = M(mu),X2(g); AHH,@, was considered and this enthalpy was calculated by means of an appropriate thermochemical cycle.…”

Section: Resultsmentioning

confidence: 99%

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Thermochemical study of adducts of methylurea with zinc, cadmium, and mercury halides

Airoldi¹,

Chagas²,

Assunção³

1982

Can. J. Chem.

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CLAUDIO AIROLDI, AECIO P. CHAGAS, and FRANCISCO P. A s s u~q i o .Can. J. Chem. 60,2132Chem. 60, (1982. The adducts Zn(mu),X, (X = CI, Br), M(mu)X, (M = Cd, Hg and X = CI, Br) have been characterized. The CO and NH stretching frequencies indicate that methylurea (mu) is bound to metals through oxygen. Enthalpies of dissolution of the adducts in ethanol or methanol have been measured calorimetrically. Combination with the enthalpies of solution of metal halides and ligand in the same solvents at 298.15 K yielded the standard enthalpy (AH,e/kJ mol-I) for the reaction: MX,(s) + nmu(s) -t M(mu),,X, (s):Zn(mu),Cl,, (-36.27k0.51); Zn(mu),Br,, (-37.52k0.97); Cd(mu)CI,, (-22.78k0.26); Cd(mu)Br,, (-9.58k0.26); Hg(mu)Cl,, (-13.91k 0.41); and Hg(mu)Br,, (-13.29k0.48). The standard enthalpies of formation of theadducts in the same sequence as above, AH,e (s, 298.15 K): -1024, -938, -70 1, -612, -524, and -470 kJ mol-', were determined from these values, the standard enthalpy of the ligand (-285k 15 kJ mol-I) being obtained via combustion calorimetry, and literature values of the standard enthalpies of metal halides being used. With the determination of the standard enthalpy of sublimation of the ligand (78.2 kJ mol-I) it was possible to determine the standard enthalpies of the reactions MX,(g)The enthalpies of metal-oxygen bonds were also estimated. Introductioninfrared studies methylurea has a nearly planar Our interest in the thermochemistry of adducts configuration of the N-C(ObN moiety with the of halides of the zinc family with urea derivatives as C-N bonds possessing appreciable double bond ligand is now focused on methylurea (mu). The character and a tendency to form hydrogen bonds determinations of crystallographic parameters for (4). It can act as a ligand utilizing either nitrogen or Cd(mu),,X, (X = C1, Br, I and n = 1, 2) and Oxygen as the d~n o r atomZn(rnu),Br, were the pioneer studies involvingFrom the results on thermal decomposition of methylurea as a ligand (1,2). Moreover, a complete CdLC1, (L = urea, and N,N'-di-X-ray diffraction pattern for Cd(mu)Cl, illustrates methylurea) adducts by therm~~ravimetric analyan interesting structure (3) where the metal is sis in air and vacuum, the following order of octahedrally coordinated, with the participation of stability was established: urea > methylurea > methylurea as a monodentate ligand. This polymer N,Nf-dimethylurea (6). his sequence clearly instructure shows one site of coordination occupied dicates an influence of ligand substituents on stabilby oxygen of the ligand carbonyl with the other ity. This is the only thermochemical datum dealing positions being occupied by chloride bridges.with the methylurea ligand. The coordination characteristic of methylurea is In Our study, the Zn(mu)*X, (X = C 1 j Br) and expected to be the same as that of N,N'-M(mu)X, (M = Cd, Hg and X = C1, Br) adducts dimethylurea (dmu) where both molecules resem-were synthesized and characterized, with special ble the urea molecule (4, 5 ) in structure. prom concern being devoted to ...

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Section: Resultsmentioning

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Thermochemical study of adducts of methylurea with zinc, cadmium, and mercury halides

Airoldi¹,

Chagas²,

Assunção³

1982

Can. J. Chem.

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“…Structures of the type [M{(C 6 H 5 ) 3 PO} 2 Cl 2 ] with M = Co II (Mangion et al, 1976) and M = Cu II (Bertrand & Kalyanaraman, 1971) had previously been investigated. Studies on the IR spectra of compounds with M = Zn II by Deacon & Green (1968, 1969, as well as the thermochemistry of M = Zn II , Cd II , Hg II investigated by Jorge et al (1978) give us valuable information as to whether the calculated bond strengths are in good agreement with experimental data.…”

Section: Commentmentioning

confidence: 99%

Dichlorobis(triphenylphosphine oxide)zinc(II) tetrahydrofuran disolvate

2001

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ChemInform Abstract: THERMOCHEMISTRY OF DICHLOROBIS(TRIPHENYLPHOSPHINE OXIDE)‐ZINC(II), ‐CADMIUM(II), AND ‐MERCURY(II)

Jorge¹,

Airoldi²,

Chagas³

1978

Chemischer Informationsdienst

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Thermochemistry of dichlorobis(triphenylphosphine oxide)-zinc(II), -cadmium(II), and -mercury(II)

Abstract: Thermochemistry of Dichlorobis(tripheny1phosphine oxide)-zinc(ii), -cadmium(ii), and -mercury(ii)

Cited by 31 publications

References 0 publications

Thermochemical study of adducts of methylurea with zinc, cadmium, and mercury halides

Thermochemical study of adducts of methylurea with zinc, cadmium, and mercury halides

Dichlorobis(triphenylphosphine oxide)zinc(II) tetrahydrofuran disolvate

ChemInform Abstract: THERMOCHEMISTRY OF DICHLOROBIS(TRIPHENYLPHOSPHINE OXIDE)‐ZINC(II), ‐CADMIUM(II), AND ‐MERCURY(II)

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