Manuel Temprado

University of Barcelona, Barcino, Catalonia, Spain

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Publications (66)246.29 Total impact

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    ABSTRACT: Tetrahedral [MoO4] (2-) readily binds CO2 at room temperature to produce a robust monocarbonate complex, [MoO3(k(2)-CO3)](2-), that does not release CO2 even at modestly elevated temperatures (up to 56 degrees C in solution and 70 degrees C in the solid state). In the presence of excess carbon dioxide, a second molecule of CO2 binds to afford a pseudo-octahedral dioxo dicarbonate complex, [MoO2(k(2)-CO3)(2)](2-), the first structurally characterized transition-metal dicarbonate complex derived from CO2. The monocarbonate [MoO3(k(2)-CO3)](2-) reacts with triethylsilane in acetonitrile under an atmosphere of CO2 to produce formate (69% isolated yield) together with silylated molybdate ( quantitative conversion to [MoO3(OSiEt3)], 50% isolated yield) after 22 hours at 85 degrees C. This system thus illustrates both the reversible binding of CO2 by a simple transition-metal oxoanion and the ability of the latter molecular metal oxide to facilitate chemical CO2 reduction.
    Chemical Science 10/2014; 5(5):1772. DOI:10.1039/c4sc00132j · 9.21 Impact Factor
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    ABSTRACT: The enthalpy of oxygen atom transfer (OAT) to V[(Me3SiNCH2CH2)3N], 1, forming OV[(Me3SiNCH2CH2)3N], 1-O, and the enthalpies of sulfur atom transfer (SAT) to 1 and V(N[t-Bu]Ar)3, 2 (Ar = 3,5-C6H3Me2), forming the corresponding sulfides SV[(Me3SiNCH2CH2)3N], 1-S, and SV(N[t-Bu]Ar)3, 2-S, have been measured by solution calorimetry in toluene solution using dbabhNO (dbabhNO = 7-nitroso-2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene) and Ph3SbS as chalcogen atom transfer reagents. The V-O BDE in 1-O is 6.3 ± 3.2 kcal·mol(-1) lower than the previously reported value for 2-O and the V-S BDE in 1-S is 3.3 ± 3.1 kcal·mol(-1) lower than that in 2-S. These differences are attributed primarily to a weakening of the V-Naxial bond present in complexes of 1 upon oxidation. The rate of reaction of 1 with dbabhNO has been studied by low temperature stopped-flow kinetics. Rate constants for OAT are over 20 times greater than those reported for 2. Adamantyl isonitrile (AdNC) binds rapidly and quantitatively to both 1 and 2 forming high spin adducts of V(III). The enthalpies of ligand addition to 1 and 2 in toluene solution are -19.9 ± 0.6 and -17.1 ± 0.7 kcal·mol(-1), respectively. The more exothermic ligand addition to 1 as compared to 2 is opposite to what was observed for OAT and SAT. This is attributed to less weakening of the V-Naxial bond in ligand binding as opposed to chalcogen atom transfer and is in keeping with structural data and computations. The structures of 1, 1-O, 1-S, 1-CNAd, and 2-CNAd have been determined by X-ray crystallography and are reported.
    Inorganic Chemistry 10/2014; 53(20). DOI:10.1021/ic5017005 · 4.76 Impact Factor
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    ABSTRACT: The transannular diphosphorus bisanthracene adduct P2A2 (A = anthracene or C14H10) was synthesized from the 7-phospha-dibenzonorbornadiene Me2NPA, through a synthetic sequence involving chlorophosphine ClPA (34%) and the tetracyclic salt [P2A2Cl][AlCl4] (65%) as isolated intermediates. P2A2 was found to transfer P2 efficiently to 1,3-cyclohexadiene (CHD), 1,3-butadiene and (C2H4)Pt(PPh3)2 to form P2(CHD)2 (>90%), P2(BD)2 (69%) and (P2)[Pt(PPh3)2]2 (47%), respectively and was characterized by X-ray diffraction as the complex [CpMo(CO)3(P2A2)][BF4]. Experimental and computational thermodynamic activation parameters for the thermolysis of P2A2 in a solution containing different CHD amounts (0, 4.75 and 182 equiv) have been obtained, and suggest that P2A2 thermally transfers P2 to CHD through two competitive routes: (i) an associative pathway in which reactive intermediate [P2A] adds the first molecule of CHD before departure of the second anthracene, and (ii) a dissociative pathway in which [P2A] fragments to P2 and A prior to addition of CHD. Additionally, a molecular beam mass spectroscopy study on the thermolysis of solid P2A2 reveals the direct detection of molecular fragments of only P2 and anthracene thus establishing a link between solution-phase P2-transfer chemistry and production of gas-phase P2 by mild thermal activation of a molecular precursor.
    Journal of the American Chemical Society 09/2014; 136(39). DOI:10.1021/ja507922x · 12.11 Impact Factor
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    ABSTRACT: Enthalpies of vaporization of 2- and 3-methoxythiophenes (48.32 +/- 0.30 and 48.54 +/- 0.22 kJ.mol (1), respectively) have been measured by the transpiration method using nitrogen as the carrying and protecting stream. Combustion experiments leading to enthalpies of formation in the liquid phase, Delta H-f(0) m(l), for both isomers failed due to rapid darkening of freshly distilled samples even under a protecting atmosphere. However, combination of experimental vaporization enthalpies with values of the gaseous enthalpies of formation, Delta H-f(m)0(g), obtained by quantum-chemical calculations from our previous work Notario et al. (2012) [24] permits establishing estimated Delta H-f(m)0(l) values of -(68.3 +/- 4.2) and -(80.1 +/- 4.2) kJ.mol (1), for 2- and 3-methoxythiophene, respectively.
    The Journal of Chemical Thermodynamics 06/2014; 73:97-100. DOI:10.1016/j.jct.2013.11.003 · 2.68 Impact Factor
  • Miguel Galajov · Carlos Garcia · Manuel Gomez · Pilar Gomez-Sal · Manuel Temprado ·
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    ABSTRACT: Reaction of alkyl imido [MTp*XR(NtBu)] (M = Nb/Ta; Tp* = HB(3,5-Me2C3HN2)(3); X = Cl, R = Me (1a/1b), CH2CH3 (2a/2b), CH2Ph (3a/3b), CH(2)tBu (4a/4b), CH2SiMe3 (5a/5b), CH2CMe2Ph (6a/6b); X = R = Me (7a/7b)) complexes with 1 equiv of the isocyanide 2,6-Me2C6H3NC takes place with migration of an alkyl group and leads to the formation of the series of chlorido or methyl imido iminoacyl derivatives [MTp*X(NtBu){C(R)NAr-kappa C-2,N}] (M = Nb/Ta; Ar = 2,6-Me2C6H3; X = Cl, R= Me (8a/8b), CH2CH3 (9a/9b), CH2Ph (10a/10b), CH(2)tBu (11a/11b), CH2SiMe3 (12a/12b), CH2CMe2Ph (13a/13b); X = R = Me (14a/14b)). The molecular structure of 10b was determined by X-ray diffraction methods. An irreversible endo -> exo isomerization was detected by H-1 NMR in compounds 10a-13a. The insertion-isomerization reaction coordinate was computed by DFT calculations.
    Organometallics 05/2014; 33(9):2277-2286. DOI:10.1021/om5002028 · 4.13 Impact Factor
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    ABSTRACT: Reaction of N-heterocyclic carbenes (NHCs) with isocyanates yields stable zwitterionic imidates/amidates in toluene solution. These compounds were fully characterized and the crystal structures of several species were determined by X-ray crystallography. The thermochemistry of binding of these and related species was studied by solution calorimetry. Comparison is made of the enthalpies of binding of NHC to isocyanates (RNCO) and isomeric nitrile oxides (RCNO) as well as CO2. DFT calculations were performed to additionally assess the nature of bonding in these compounds.
    Structural Chemistry 12/2013; 24(6). DOI:10.1007/s11224-013-0305-2 · 1.84 Impact Factor
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    ABSTRACT: The 3,4,8,9-tetramethyl-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P2(C6H10)2) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P-P bonded λ(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSbPh3 has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)2 (87%), O2P2(C6H10)2 (94%), SP2(C6H10)2 (56%), and S2P2(C6H10)2 (87%). Computational studies indicate that the oxygen-atom transfer reactions involve penta-coordinated phosphorus intermediates that have four-membered {PONC} cycles. The P-E bond dissociation enthalpies in EP2(C6H10)2 were measured via calorimetric studies to be 134.7 ± 2.1 kcal/mol for P-O, and 93 ± 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P-P bond and formation of diphosphinate O3P2(C6H10)2 was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P2(C6H10)2(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P2(C6H10)2 (91% for R = Mes). Metalation reactions with the bulky diiminodiphosphorane ligand (MesN)2P2(C6H10)2 (nppn) allowed for the isolation and characterization of (nppn)Mo(η(3)-C3H5)Cl(CO)2 (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(η(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.
    Inorganic Chemistry 07/2013; 52(15). DOI:10.1021/ic401052a · 4.76 Impact Factor
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    ABSTRACT: Thermodynamic, kinetic and computational studies are reported for oxygen atom transfer (OAT) to the complex V(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2, 1) from compounds containing N-O bonds with a range of BDEs spanning nearly 100 kcal mol-1: PhNO (108) > SIPr/MesCNO (78) > PyO (63) > IPr/N2O (62) > MesCNO (53) > N2O (40) > dbabhNO (10) (Mes = mesityl; SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene; Py = pyridine; IPr = 1,3-bis(diisopropyl)phenylimidazol-2-ylidene; dbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene). Stopped flow kinetic studies of the OAT reactions show a range of kinetic behavior influenced by both the mode and strength of coordination of the O donor and its ease of atom transfer. Four categories of kinetic behavior are observed depending upon the magnitudes of the rate constants involved: I) Dinuclear OAT following an overall third order rate law (N2O); II) Formation of stable oxidant-bound complexes followed by OAT in a separate step (PyO and PhNO); III) Transient formation and decay of metastable oxidant-bound intermediates on the same time scale as OAT (SIPr/MesCNO and IPr/N2O); IV) Steady state kinetics in which no detectable intermediates are observed (dbabhNO and MesCNO). Thermochemical studies of OAT to 1 show that the V-O bond in O≡V(N[t-Bu]Ar)3 is strong (BDE = 154  3 kcal mol-1) compared to all the N-O bonds cleaved. In contrast, measurement of the N-O bond in dbabhNO show it to be especially weak (BDE = 10  3 kcal mol-1) and that dissociation of dbabhNO to anthracene, N2 and a 3O atom is thermodynamically favorable at room temperature. Comparison of the OAT of adducts of N2O and MesCNO to the bulky complex 1 show a faster rate than in the case of free N2O or MesCNO in spite of increased steric hindrance of the adducts.
    Journal of the American Chemical Society 06/2013; 135(30). DOI:10.1021/ja405395z · 12.11 Impact Factor
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    ABSTRACT: Treatment of V(N[<sup>t</sup>Bu]Ar)<sub>3</sub> = 1 (Ar = 3,5-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) with O<sub>2</sub> was shown by stopped flow kinetic studies to rapidly form (η<sup>1</sup>-O<sub>2<sub>)V(N[<sup>t</sup>Bu]Ar)<sub>3</sub> = 2 (Δ H <sup>‡</sup> = 3.3 ± 0.2 kcal/mol and Δ S <sup>‡</sup> = -22 ± 1 cal/mol·K) which subsequently isomerizes to (η<sup>2</sup>-O<sub>2<sub>)V(N[<sup>t</sup>Bu]Ar)<sub>3</sub> = 3 (Δ H <sup>‡</sup> = 10.3 ± 0.9 kcal/mol and Δ S <sup>‡</sup> = -6 ± 4 cal/mol·K). The enthalpy of binding of O<sub>2</sub> to form 3 is -75.0 ± 2.0 kcal/mol as measured by solution calorimetry. Reaction of 3 and 1 to form two moles of O≡V(N[<sup>t</sup>Bu]Ar)<sub>3</sub> = 4 occurs by initial isomerization of 3 to 2 . Computational studies of this rearrangement (Δ H = 4.2 kcal/mol; Δ H <sup>‡</sup> = 16 kcal/mol) are in accord with experimental data (Δ H = 4 ± 3 kcal/mol; Δ H <sup>‡</sup> = 14 ± 3 kcal/mol). With the aim of supressing formation of 4 , the reaction of O<sub>2</sub> with 1 in the presence of <sup>t</sup>BuCN was studied. At -45 °C the principal products of this reaction are 3 and <sup>t</sup>BuC(=O)N≡V(N[<sup>t</sup>Bu]Ar)<sub>3</sub> = 5 in which the bound nitrile has been oxidized. Crystal structures of 3 and 5 are reported.
    Journal of the American Chemical Society 10/2012; 134(44). DOI:10.1021/ja309621h · 12.11 Impact Factor
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    ABSTRACT: A methodol. for the prediction of excitation energies for substituted chromophores from ground state structures was developed. The formalism introduces the concept of structural substituent excitation energy effect for the rational prediction and quantification of the substituent effect in the excitation energy of a chromophore to an excited electronic state. This effect quantifies exclusively the excitation energy variation due to the structural changes of the chromophore induced by the substituent. Therefore, excitation bathochromic and hypsochromic shifts of substituted chromophores can be predicted from known ground and excited potential energy surfaces of a ref. unsubstituted chromophore, together with the ground state min. energy structure of the substituted chromophore. This formalism can be applied if the chem. substitution does not affect the nature of the electronic excitation, where the substituent effect can be understood as a force acting on the chromophore and provoking a structural change on it. The developed formalism provides a useful tool for quant. and qual. detn. of the excitation energy of substituted chromophores and also for the anal. and detn. of the structural changes affecting this energy. The proposed methodol. was applied to the prediction of the excitation energy to the 1st bright state of several S-nitrosothiols using the potential energy surfaces of Me-S-nitrosothiol as a ref. unsubstituted chromophore. [on SciFinder(R)]
    Journal of Chemical Theory and Computation 09/2012; 8(9):3293-3302. DOI:10.1021/ct300597u · 5.50 Impact Factor
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    ABSTRACT: The photochemistry and photophysics of a series of S-nitrosothiols (RSNOs) have been studied computationally. The photocleavage mechanism of the model compound CH(3)SNO to release CH(3)S· and ·NO was studied at the CASPT2 level resulting in a barrierless process when irradiating in the visible region (S(1)), in the near UV region (S(2)) and for photosensitized (T(1)) reaction. The absorption energy required to initiate photocleavage was calculated at the CASPT2 and B3P86 levels showing the possibility of the modulation of NO release by RSNO photoactivation as a function of the substituent R. Good correlations between the wavelengths of the lowest energy (1)(n,π*) and (1)(π,π*) transitions of aryl S-nitrosothiols and the corresponding Hammett constants of the substituents have been obtained.
    The Journal of Physical Chemistry A 06/2012; 116(26):7039-49. DOI:10.1021/jp304707n · 2.69 Impact Factor
  • Rafael Notario · Manuel Temprado · María Victoria Roux · Joel F Liebman ·
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    ABSTRACT: Very good linear correlations between experimental and calculated enthalpies of formation in the gas phase (G3(MP2)//B3LYP and G3) for 48 thiophene derivatives have been obtained. These correlations permit a correction of the calculated enthalpies of formation in order to estimate more reliable "experimental" values for the enthalpies of formation of substituted thiophenes, check the reliability of experimental measurements, and also predict the enthalpies of formation of new thiophenes that are not available in the literature. Moreover, the difference between the enthalpies of formation of isomeric thiophenes with the same substituent in positions 2 and 3 of the ring has been analyzed. Likewise, a comparison of the substituent effect in the thiophene and benzene rings has been established.
    The Journal of Physical Chemistry A 04/2012; 116(17):4363-70. DOI:10.1021/jp300857v · 2.69 Impact Factor
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    ABSTRACT: Heterometallic aluminium-lithium species were prepared by the fragmentation reaction of the hexametallic cage compound [Li{2,6-(MeO)(2)C(6)H(3)O}](6) (1) with alkyl aluminium derivatives. Depending on the aluminium precursor, the species formed present different nuclearities in the solid state as shown by single crystal X-ray analysis. Spectroscopic and computational studies have been performed to study the nuclearity of the synthesized compounds in solution.
    Chemical Communications 09/2011; 47(42):11757-9. DOI:10.1039/c1cc14577k · 6.83 Impact Factor
  • Maria Victoria Roux · Manuel Temprado · Pilar Jiménez · Rafael Notario ·
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    ABSTRACT: In a continuation of our investigations of the thermochemistry of heterocyclic ring systems and sulfur-containing compounds, the standard molar enthalpy of formation of tetrahydro-2H-1,3-oxazine-2-thione (CAS no. 17374-18-4) at T = 298 K has been evaluated both experimentally and computationally. Combined enthalpies of combustion and sublimation, measured by rotary bomb combustion calorimetry and the Knudsen effusion technique, yielded a gas-phase enthalpy of formation of −(104.0 ± 5.5) kJ·mol–1. The G3 value of −104.6 kJ·mol–1 calculated using an isodesmic bond separation reaction is in excellent agreement with the experimental result. The variation in enthalpy of formation with ring size is discussed, and the G3 enthalpy of formation of tetrahydro-2H-1,3-thiazine-2-thione (72.4 kJ·mol–1) was also computed for this purpose.
    Journal of Chemical & Engineering Data 09/2011; 56(12). DOI:10.1021/je200549z · 2.04 Impact Factor
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    ABSTRACT: The enthalpies of oxygen atom transfer (OAT) from mesityl nitrile oxide (MesCNO) to Me(3)P, Cy(3)P, Ph(3)P, and the complex (Ar[(t)Bu]N)(3)MoP (Ar = 3,5-C(6)H(3)Me(2)) have been measured by solution calorimetry yielding the following P-O bond dissociation enthalpy estimates in toluene solution (±3 kcal mol(-1)): Me(3)PO [138.5], Cy(3)PO [137.6], Ph(3)PO [132.2], (Ar[(t)Bu]N)(3)MoPO [108.9]. The data for (Ar[(t)Bu]N)(3)MoPO yield an estimate of 60.2 kcal mol(-1) for dissociation of PO from (Ar[(t)Bu]N)(3)MoPO. The mechanism of OAT from MesCNO to R(3)P and (Ar[(t)Bu]N)(3)MoP has been investigated by UV-vis and FTIR kinetic studies as well as computationally. Reactivity of R(3)P and (Ar[(t)Bu]N)(3)MoP with MesCNO is proposed to occur by nucleophilic attack by the lone pair of electrons on the phosphine or phosphide to the electrophilic C atom of MesCNO forming an adduct rather than direct attack at the terminal O. This mechanism is supported by computational studies. In addition, reaction of the N-heterocyclic carbene SIPr (SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene) with MesCNO results in formation of a stable adduct in which the lone pair of the carbene attacks the C atom of MesCNO. The crystal structure of the blue SIPr·MesCNO adduct is reported, and resembles one of the computed structures for attack of the lone pair of electrons of Me(3)P on the C atom of MesCNO. Furthermore, this adduct in which the electrophilic C atom of MesCNO is blocked by coordination to the NHC does not undergo OAT with R(3)P. However, it does undergo rapid OAT with coordinatively unsaturated metal complexes such as (Ar[(t)Bu]N)(3)V since these proceed by attack of the unblocked terminal O site of the SIPr·MesCNO adduct rather than at the blocked C site. OAT from MesCNO to pyridine, tetrahydrothiophene, and (Ar[(t)Bu]N)(3)MoN was found not to proceed in spite of thermochemical favorability.
    Inorganic Chemistry 08/2011; 50(19):9620-30. DOI:10.1021/ic2013599 · 4.76 Impact Factor
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    ABSTRACT: This paper reports an experimental and computational thermochemical study on 1,3-dimethylbarbituric acid. The value of the standard (p° = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K has been determined. The energy of combustion was measured by static bomb combustion calorimetry, and from the result obtained, the standard molar enthalpy of formation in the crystalline state at T = 298.15 K was calculated as -639.6 ± 1.9 kJ·mol(-1). The enthalpy of sublimation was determined using a transference (transpiration) method in a saturated N(2) stream and a value of the enthalpy of sublimation at T = 298.15 K was derived as 92.3 ± 0.6 kJ·mol(-1). From these results a value of -547.3 ± 2.0 kJ·mol(-1) for the gas-phase enthalpy of formation at T = 298.15 K was determined. Theoretical calculations at the G3 and G4 levels were performed, and a study on molecular and electronic structure of the compound has been carried out. Calculated enthalpies of formation are in very good agreement with the experimental value.
    The Journal of Physical Chemistry A 03/2011; 115(14):3167-73. DOI:10.1021/jp200562m · 2.69 Impact Factor
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    ABSTRACT: The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR(3)) complexes with O(2) has been examined. Stopped-flow kinetic studies show that O(2) binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))(η(2)-O(2))] occurs in a rapid, second-order process. The enthalpy of O(2) binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(η(2)-O(2))] but to paramagnetic trans-[(Pd(IPr)(2)(η(1)-O(2))(2)], which has been fully characterized. Computational studies addressing the energetics of O(2) binding have been performed and provide insight into reactivity changes as steric pressure is increased.
    Journal of the American Chemical Society 02/2011; 133(5):1290-3. DOI:10.1021/ja1103348 · 12.11 Impact Factor
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    ABSTRACT: The present study reports a differential scanning calorimetry (DSC) study of the barbituric acid derivatives: 1,3-dimethylbarbituric acid [CAS 769-42-6], 5,5-dimethylbarbituric acid [CAS 24448-94-0], 1,3-diethylbarbituric acid [CAS 32479-73-5], 1,3,5-trimethylbarbituric acid [CAS 7358-61-4], 1,5,5-trimethylbarbituric acid [CAS 702-47-6], and tetramethylbarbituric acid [CAS 13566-66-0] in the temperature interval from T = 268 K to their respective melting temperatures. Temperatures, enthalpies and entropies of fusion, and the heat capacities of the solid compounds as a function of temperature are reported.
    Journal of Chemical & Engineering Data 12/2010; 56(2). DOI:10.1021/je1008944 · 2.04 Impact Factor
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    ABSTRACT: This paper reports an experimental and theoretical study of the structures and standard (p(o) = 0.1 MPa) molar enthalpies of formation of 3H-1,3-benzoxazole-2-thione and 3H-1,3-benzothiazole-2-thione. The enthalpies of combustion and sublimation were measured by rotary bomb combustion calorimetry and the Knudsen effusion technique, and gas-phase enthalpies of formation values at T = 298.15 K of (42.0 +/- 2.7) and (205.5 +/- 3.8) kJ x mol(-1) for 3H-1,3-benzoxazole-2-thione and 3H-1,3-benzothiazole-2-thione, respectively, were determined. G3-calculated enthalpies of formation are in excellent agreement with the experimental values. The present work discusses the question of tautomerism explicitly for both compounds and compares the energetics of all the related species. A comparison of the theoretical results with the structural data is also reported.
    The Journal of Physical Chemistry A 06/2010; 114(21):6336-41. DOI:10.1021/jp102126j · 2.69 Impact Factor
  • Tamás Kégl · George C. Fortman · Manuel Temprado · Carl D. Hoff ·

    Physical Inorganic Chemistry: Reactions, Processes, and Applications, 04/2010: pages 429 - 494; , ISBN: 9780470602577

Publication Stats

873 Citations
246.29 Total Impact Points


  • 2014
    • University of Barcelona
      • Department Analytical Chemistry
      Barcino, Catalonia, Spain
  • 2011-2014
    • Hospital Universitario Henares
      Madrid, Madrid, Spain
  • 2010-2014
    • University of Alcalá
      • • Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering
      • • Department of Organic and Inorganic Chemistry
      Cómpluto, Madrid, Spain
  • 2002-2011
    • Institute of Physical Chemistry Rocasolano
      Madrid, Madrid, Spain
  • 2009-2010
    • University of Miami
      • Department of Chemistry
      Coral Gables, FL, United States
  • 2002-2010
    • Spanish National Research Council
      • Institute of Physical Chemistry "Rocasolano"
      Madrid, Madrid, Spain
  • 2008-2009
    • Massachusetts Institute of Technology
      Cambridge, Massachusetts, United States
  • 2005
    • University of Missouri - St. Louis
      • Department of Chemistry and Biochemistry
      Сент-Луис, Michigan, United States