First Principle Attempt towards the Thermodynamic Stability of Telluroformaldehyde and its Heavier Analogs: H(2-n)X(n)A=Te (X=H, F, Cl and Br; A=C, Si and Ge; n=0-2)

Abstract H(2-n)X(n)A=Te (X=H, F, Cl and Br; A=C, Si and Ge; n=0-2), the novel heavy congeners of formaldehyde, have been studied in the gas phase using MP2/def2-TVZP and BP86/def2-TVZP methods. Emphasis has been laid on the bond strengths and the standard heats of formation (ΔHf°) of the mentioned telluro -ketones to reveal their thermodynamic stabilities and further assist in their isolations. The bond strengths have been evaluated in terms of the σ-bond energy, π-bond energy and the bond dissociation enthalpy, D°, using isodesmic reaction schemes. The methodology employed has satisfactorily reproduced the bond strengths and the ΔHf° of formaldehyde and silanone. The findings from this work indicate that the D° of the F2A=Te (A=C, Si and Ge) molecules are comparable to that of H2C=O and thus their respective stabilities are expected to be equivalent to that of formaldehyde. Besides, the fluorinated telluro -ketones are predicted to possess a unique thermodynamic stability since they have the most exothermic ΔHf° in their respective series while the H2A=Te ketones have the most endothermic ΔHf°. In addition, the silanetellones are found to be thermodynamically more stable than their corresponding telluroformaldehyde and germanetellone analogs. Since reported data for H(2-n)X(n)A=Te (X=H, F, Cl and Br; A=C, Si and Ge; n=0-2) is non-existent in terms of the thermodynamic data, the findings of this work should supplement the literature with reliable information.

[1]  H. Bockhorn,et al.  Thermodynamic and ab initio analysis of the controversial enthalpy of formation of formaldehyde. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[2]  S. Nagase,et al.  SYNTHESIS, STRUCTURE, AND REACTIVITY OF THE FIRST KINETICALLY STABILIZED SILANETHIONE , 1998 .

[3]  H. Schaefer,et al.  Predicting molecules--more realism, please! , 2008, Angewandte Chemie.

[4]  D. W. Ball.  Carbonyl diazide, OC(N3)2: Calculated thermodynamic properties , 2011 .

[5]  P. Schleyer,et al.  A comparison of the energies of double bonds of second-row elements with carbon and silicon , 1988 .

[6]  H. Stoll,et al.  Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post-d group 16–18 elements , 2003 .

[7]  T. Iwamoto,et al.  Synthesis, properties, and reactions of a series of stable dialkyl-substituted silicon-chalcogen doubly bonded compounds. , 2006, Journal of the American Chemical Society.

[8]  Kent Milfeld,et al.  From Proposal to Production: Lessons Learned Developing the Computational Chemistry Grid Cyberinfrastructure , 2006, Journal of Grid Computing.

[9]  H. Rosenstock,et al.  Energetics of Gaseous Ions , 1976 .

[10]  Melita L. Morton,et al.  IUPAC Critical Evaluation of Thermochemical Properties of Selected Radicals. Part I , 2005 .

[11]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[12]  C. Headford,et al.  Reactions of osmium coordinated formaldehyde. Synthesis of complexes of selenoformaldehyde and telluroformaldehyde , 1983 .

[13]  Frank Weinhold,et al.  Natural hybrid orbitals , 1980 .

[14]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[15]  Robin Walsh,et al.  Bond dissociation energy values in silicon-containing compounds and some of their implications , 1981 .

[16]  M. Binnewies,et al.  Formation and stability of molybdenum-tellurium oxides MoTeO5, Mo2TeO8, Mo3TeO11 and MoTe2O7 in the gas phase. Quantum chemical and mass spectrometry determination of standard enthalpy of formation. , 2012, Dalton transactions.

[17]  S. Nagase,et al.  The First Genuine Silicon-Sulfur Double-Bond Compound: Synthesis and Crystal Structure of a Kinetically Stabilized Silanethione , 1994 .

[18]  Chien-Nan Lin,et al.  Recent progress in the chemistry of anionic groups 6–8 carbonyl chalcogenide clusters , 2012 .

[19]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .

[20]  N. Tokitoh,et al.  The First Kinetically Stabilized Germanethiones and Germaneselones: Syntheses, Structures, and Reactivities , 1999 .

[21]  Krishnan Raghavachari,et al.  Gaussian‐1 theory of molecular energies for second‐row compounds , 1990 .

[22]  S. Grimme,et al.  Why the standard B3LYP/6-31G* model chemistry should not be used in DFT calculations of molecular thermochemistry: understanding and correcting the problem. , 2012, The Journal of organic chemistry.

[23]  H. Stoll,et al.  Energy-adjustedab initio pseudopotentials for the second and third row transition elements , 1990 .

[24]  D. Hashizume,et al.  A stable germanone as the first isolated heavy ketone with a terminal oxygen atom. , 2012, Nature chemistry.

[25]  G. A. Petersson,et al.  Computational study of the properties and reactions of small molecules containing O, S, and Se. , 2011, The journal of physical chemistry. A.

[26]  L. Curtiss,et al.  Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint , 1988 .

[27]  M. Matos,et al.  Experimental and computational thermochemistry of 6,7-dihydro-4(5H)-benzofuranone , 2013 .

[28]  Krishnan Raghavachari,et al.  Gaussian-2 theory for molecular energies of first- and second-row compounds , 1991 .

[29]  Naziah B. Jaufeerally,et al.  Erratum to: Telluroformaldehyde and its derivatives: structures, ionization potentials, electron affinities and singlet–triplet gaps of the X2CTe and XYCTe (X,Y = H, F, Cl, Br, I and CN) species , 2012, Theoretical Chemistry Accounts.

[30]  G. Frenking,et al.  Donor-acceptor stabilized silaformyl chloride. , 2012, Chemical communications.

[31]  L. Curtiss,et al.  Gaussian-3 (G3) theory for molecules containing first and second-row atoms , 1998 .

[32]  Frank Weinhold,et al.  Natural bond orbital analysis of near‐Hartree–Fock water dimer , 1983 .

[33]  R. Okazaki,et al.  THE FIRST KINETICALLY STABILIZED STANNANESELONE AND DISELENASTANNIRANE: SYNTHESIS BY DESELENATION OF A TETRASELENASTANNOLANE AND STRUCTURES , 1997 .

[34]  H. Schlegel,et al.  Heats of formation of silicon hydride oxide (SiHnO and SiHnO2) calculated by ab initio molecular orbital methods at the G-2 level of theory , 1993 .

[35]  Kent Milfeld,et al.  Cluster Computing through an Application-oriented Computational Chemistry Grid , 2005 .

[36]  L. Curtiss,et al.  Gaussian-4 theory. , 2007, The Journal of chemical physics.

[37]  L. Curtiss,et al.  Gaussian‐1 theory: A general procedure for prediction of molecular energies , 1989 .

[38]  Novel silanetellones: Structures, ionization potentials, electron affinities, singlet–triplet gaps and Kohn–Sham HOMO–LUMO gaps of the X2SiTe and XYSiTe (X, Y = H, F, Cl, Br, I and CN) molecules , 2013 .

[39]  J. Waters,et al.  A mononuclear, low-valent, electron-rich osmium methylene complex , 1983 .