Radical and Molecular Processes in the Thermal Decomposition of Trimethyl and Triethyl Stibines

Berrigan, R.; Metson, James B.; Russell, David L.

doi:10.1002/(sici)1521-3862(199801)04:01<23::aid-cvde23>3.0.co;2-q

Cited by 5 publications

(9 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…18 On the other hand, a number of recent high-level theoretical investigations have thrown new light on possible reaction routes. [19][20][21][22][23][24] We have shown that the technique of infrared laser powered homogeneous pyrolysis (IR LPHP), allied with standard mechanistic tools such as matrix isolation spectroscopies, reaction in the presence of trapping agents, and ab initio or semiempirical calculation of activation energies, can provide unique insights into the mechanisms of pyrolysis in systems as varied as azines, 25 organometallic chemical vapour deposition (CVD) precursors, [26][27][28][29][30][31] glycine 32 and chlorofluorocarbons. 33 In particular, the use of matrix isolation EPR spectroscopy and of radical traps such as H 2 or D 2 allows the disentanglement of molecular and radical pathways.…”

Section: Introductionmentioning

confidence: 99%

The thermal decomposition of 5-membered rings: a laser pyrolysis study

Hore

Russell

2004

New J. Chem.

Self Cite

View full text Add to dashboard Cite

The mechanisms of pyrolysis of cyclopentadiene, furan, pyrrole and thiophene have been investigated using a combination of IR laser powered homogeneous pyrolysis, chemical and physical trapping of radical intermediates, and use of precursors specifically designed to generate selected radical intermediates. The results confirm the central role played by free radicals in the cases of cyclopentadiene and thiophene, and the dominant step of 1,2-H shifts in the cases of furan and pyrrole. The experimental results may be interpreted according to the high level ab initio calculations recently reported in the literature. NJC

show abstract

Section: Introductionmentioning

confidence: 99%

The thermal decomposition of 5-membered rings: a laser pyrolysis study

Hore

Russell

2004

New J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…At typical CVD temperatures (200−600 °C) the L 2 species is more stable for each of the five ligands explored in this study (the first L 2 molecule to thermally cleave is H 2 O 2 , which dissociates to form 2OH • above ∼1650 K) with the resulting methyl radicals abstracting a hydrogen atom from Sb(CH 3 ) 3 to form methane and Sb(CH 3 ) 2 (CH 2 ) …”

Section: Resultsmentioning

confidence: 98%

“…16 An additional study with EPR detection of radical species expanded these results for Sb(CH 3 ) 3 and Sb(C 2 H 5 ) 3 , proposing that the initial ligand eliminated is a radical, L‚, that is terminated by abstracting a proton from other SbL 3 molecules. 17 When modeling the species present within a chemical vapor deposition (CVD) reactor, the thermochemical quantities of greatest interest are the molecular heats of formation, which permit calculation of reaction enthalpies and bond dissociation energies (BDEs). For processes such as pyrolysis where the number of molecules present changes during the reaction, entropic contributions to reaction spontaneity become important, necessitating consideration of reaction free energy and its variation with temperature.…”

Section: Introductionmentioning

confidence: 99%

BAC-MP4 Predictions of Thermochemistry for Gas-Phase Antimony Compounds in the Sb−H−C−O−Cl System

Allendorf

Melius

2006

J. Phys. Chem. A

View full text Add to dashboard Cite

Calibrated by both experimental data and high-level coupled-cluster calculations, the BAC-MP4 methodology was applied to 51 SbL(n) (L = H, CH(3), C(2)H(5), Cl, and OH, n = 1-5) molecules, providing calculated heats of formation and associated thermodynamic parameters. These data identify a linear variation in heats of formation with ligand substitution, trends in bond dissociation energies (BDEs) with ligand identity [BDE(Sb-C(2)H(5)) < BDE(Sb-CH(3)) < BDE(Sb-H) < BDE(Sb-Cl) < BDE(Sb-OH)], and a monotonic decrease in BDE upon successive ligand elimination. The linear variation in BDE is consistent with the behavior of other group V elements, in contrast to the characteristic high-low-high trend of adjacent group III (In) and group IV (Sn) elements. Additionally, these data complement those of previous studies of metal-organic species and provide a foundation of thermochemical data that can aid in the selection of CVD precursors and deposition conditions for the growth of antimony-containing materials.

show abstract

“…5,6 When allied with standard analytical methods and augmented by techniques for the detection and identification of short-lived reaction intermediates and ab initio evaluation of the feasibility of reaction routes, very detailed information may be obtained. The value of this multilateral approach has been demonstrated in systems as varied as precursors to chemical vapour deposition, [7][8][9][10][11] various cyclic systems 12,13 and small organic molecules. 14 In the present work, we report IR LPHP studies of the three common diketones acacH, 1,1,1,5,5,5-hexafluoropentane-2,4dione (hexafluoroacetylacetone, hfacH, 2), and 2,2,6,6-tetramethylheptane-3,5-dione (thdH, 3).…”

Section: Introductionmentioning

confidence: 99%

Laser pyrolysis studies of β-diketonate chemical vapour deposition precursors. Part 1: β-diketones

Russell

Yee

2005

New J. Chem.

Self Cite

View full text Add to dashboard Cite

The thermal decomposition of the b-diketones pentane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, and 2,2,6,6-tetramethylheptane-3,5-dione has been studied using the technique of IR laser-powered homogeneous pyrolysis combined with the ab initio calculation of activation energies of possible reaction pathways. Pentane-2,4-dione decomposes by two parallel molecular elimination pathways, the keto tautomer affording acetone and ketene via a 6-electron retroene reaction and the enol tautomer 2-methylfuran via H 2 O elimination, followed by cyclisation. 1,1,1,5,5,5-Hexafluoropentane-2,4-dione eliminates HF with ring closure to yield 2,2-difluoro-5-(trifluoromethyl)furan-3(2H)-one. There is also a minor route of loss of one or two CF 3 radicals, followed by H-abstraction to yield 3,3-difluoroacryloylfluoride and carbon suboxide, respectively. 2,2,6,6-Tetramethylheptane-3,5-dione decomposes via central C-CO bond homolysis, followed by CO or ketene loss from the resultant radicals and subsequent disproportionation of t-Bu radicals to produce 2-methylpropene and 2-methylpropane.

show abstract

Radical and Molecular Processes in the Thermal Decomposition of Trimethyl and Triethyl Stibines

Cited by 5 publications

References 23 publications

The thermal decomposition of 5-membered rings: a laser pyrolysis study

The thermal decomposition of 5-membered rings: a laser pyrolysis study

BAC-MP4 Predictions of Thermochemistry for Gas-Phase Antimony Compounds in the Sb−H−C−O−Cl System

Laser pyrolysis studies of β-diketonate chemical vapour deposition precursors. Part 1: β-diketones

Contact Info

Product

Resources

About