A combined crossed molecular beams and ab initio investigation on the formation of vinylsulfidoboron (C2H311B32S)

Yang, Tao; Dangi, Beni B.; Parker, Dorian S. N.; Kaiser, Ralf I.; An, Yi; Chang, Agnes H. H.

doi:10.1039/c4cp01651c

Cited by 6 publications

(7 citation statements)

References 55 publications

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“…This holds in particular for bimolecular reactions between diatomic radicals and small hydrocarbons. Bimolecular reactions involving diatomic radicals such as boron monoxide (BO), [28][29][30][31][32][33][34][35] boron monosulfide (BS), [36][37] methylidyne (CH/CD), [38][39][40][41][42][43][44][45] cyano (CN), 32,[46][47][48][49][50][51][52][53][54][55][56][57][58][59][60] dicarbon (C 2 ), 57,[61][62][63][64][65][66][67][68][69][70][71][72][73][74] hydroxyl (OH), [75]…”

Section: Introductionmentioning

confidence: 99%

“…This holds in particular for bimolecular reactions between diatomic radicals and small hydrocarbons. Bimolecular reactions involving diatomic radicals such as boron monoxide (BO), 28−35 boron monosulfide (BS), 36,37 methylidyne (CH/CD), 38−45 cyano (CN), 32,46−60 dicarbon (C 2 ), 57,61−74 hydroxyl (OH), 75−86 silicon nitride (SiN) 32 and silylidyne (SiH/SiD), 87 synthesized important transient species in extreme environments ranging from low temperature molecular clouds to high temperature combustion settings, interstellar, and chemical vapor deposition environments (Table 1). Among these diatomic radicals, reactions of the silylidyne radical (SiH; X 2 Π) with hydrocarbons have received particular attention as these bimolecular reactions are expected to result in the formation of small organosilicon molecules (SiC x H y , x ≤ 6, y ≤ 6).…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X²Π) with Methylacetylene (CH₃CCH; X¹A₁) and D4-Methylacetylene (CD₃CCD; X¹A₁)

et al. 2016

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The bimolecular gas-phase reactions of the ground-state silylidyne radical (SiH; X(2)Π) with methylacetylene (CH3CCH; X(1)A1) and D4-methylacetylene (CD3CCD; X(1)A1) were explored at collision energies of 30 kJ mol(-1) under single-collision conditions exploiting the crossed molecular beam technique and complemented by electronic structure calculations. These studies reveal that the reactions follow indirect scattering dynamics, have no entrance barriers, and are initiated by the addition of the silylidyne radical to the carbon-carbon triple bond of the methylacetylene molecule either to one carbon atom (C1; [i1]/[i2]) or to both carbon atoms concurrently (C1-C2; [i3]). The collision complexes [i1]/[i2] eventually isomerize via ring-closure to the c-SiC3H5 doublet radical intermediate [i3], which is identified as the decomposing reaction intermediate. The hydrogen atom is emitted almost perpendicularly to the rotational plane of the fragmenting complex resulting in a sideways scattering dynamics with the reaction being overall exoergic by -12 ± 11 kJ mol(-1) (experimental) and -1 ± 3 kJ mol(-1) (computational) to form the cyclic 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4; p1). In line with computational data, experiments of silylidyne with D4-methylacetylene (CD3CCD; X(1)A1) depict that the hydrogen is emitted solely from the silylidyne moiety but not from methylacetylene. The dynamics are compared to those of the related D1-silylidyne (SiD; X(2)Π)-acetylene (HCCH; X(1)Σg(+)) reaction studied previously in our group, and from there, we discovered that the methyl group acts primarily as a spectator in the title reaction. The formation of 2-methyl-1-silacycloprop-2-enylidene under single-collision conditions via a bimolecular gas-phase reaction augments our knowledge of the hitherto poorly understood silylidyne (SiH; X(2)Π) radical reactions with small hydrocarbon molecules leading to the synthesis of organosilicon molecules in cold molecular clouds and in carbon-rich circumstellar envelopes.

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“…This holds in particular for bimolecular reactions between diatomic radicals and small hydrocarbons. Bimolecular reactions involving diatomic radicals such as boron monoxide (BO), [28][29][30][31][32][33][34][35] boron monosulfide (BS), [36][37] methylidyne (CH/CD), [38][39][40][41][42][43][44][45] cyano (CN), 32,[46][47][48][49][50][51][52][53][54][55][56][57][58][59][60] dicarbon (C 2 ), 57,[61][62][63][64][65][66][67][68][69][70][71][72][73][74] hydroxyl (OH), [75]…”

Section: Introductionmentioning

confidence: 99%

“…This holds in particular for bimolecular reactions between diatomic radicals and small hydrocarbons. Bimolecular reactions involving diatomic radicals such as boron monoxide (BO), 28−35 boron monosulfide (BS), 36,37 methylidyne (CH/CD), 38−45 cyano (CN), 32,46−60 dicarbon (C 2 ), 57,61−74 hydroxyl (OH), 75−86 silicon nitride (SiN) 32 and silylidyne (SiH/SiD), 87 synthesized important transient species in extreme environments ranging from low temperature molecular clouds to high temperature combustion settings, interstellar, and chemical vapor deposition environments (Table 1). Among these diatomic radicals, reactions of the silylidyne radical (SiH; X 2 Π) with hydrocarbons have received particular attention as these bimolecular reactions are expected to result in the formation of small organosilicon molecules (SiC x H y , x ≤ 6, y ≤ 6).…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X²Π) with Methylacetylene (CH₃CCH; X¹A₁) and D4-Methylacetylene (CD₃CCD; X¹A₁)

et al. 2016

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“…Based on a recommendation by Pyykko on the nature of multiple bonds, the boron–oxygen bonds of all boronyls illustrated here should be considered as triple bond, as they are shorter than 135 pm, a distance identified as representative of a boron–oxygen double bond. The extracted generalized concepts of a barrierless addition–hydrogen/methyl elimination and overall exoergic reaction are now being applied to elucidate the reaction dynamics of hitherto even more exotic systems: the formation of organic boronyl sulfides (RBS). , The reactions of the isovalent boronyl sulfide radical (BS) are conducted with unsaturated hydrocarbons such as acetylene and ethylene under single collision conditions accessing the previously elusive class of boronyl sulfides under collisionless conditions thus exploring the class of strange, new boronyl sulfides.…”

Section: Discussionmentioning

confidence: 99%

Exploring the Gas Phase Synthesis of the Elusive Class of Boronyls and the Mechanism of Boronyl Radical Reactions under Single Collision Conditions

Kaiser

Balucani

2016

Acc. Chem. Res.

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Until recently, the chemistry of boronyl (BO), a diatomic radical isolectronic with the cyano (CN) species, has remained unknown. The boronyl group is characterized by a boron-oxygen multiple bond, and because of the inherent electron deficiency of the boron atom, boronyls (RBO) are highly reactive and typically only exist in their cyclotrimeric form (RBO). Due to their invaluable role as reactants, the isolation of the monomers in gas phase experiments has been extensively sought after by the organic synthesis and physical organic chemistry communities but never achieved. Besides the interests from a physical organic and synthetic point of view, boronyls also play a role as reaction intermediates in boron-assisted rocket propulsion systems. In this Account, we review recent experimental work in which gas phase organo boronyl monomers (RBO) are formed via bimolecular reactions of the boronyl radical (BO) with C2-C6 unsaturated hydrocarbons. The investigated hydrocarbons are widely exploited as fuels, and their reactions with boronyl radicals under single collision conditions lead to the formation of organo boronyls. Our studies also elucidate the mechanisms of their formation reactions thus furnishing a comprehension at the molecular level of this reaction class. The variety of the employed hydrocarbon substrates has allowed us to systematically classify the chemical behavior of the boronyl radicals. With the exception of the case of the dimethylacetylene reaction, the boron monoxide radical versus atomic hydrogen exchange mechanisms were always open leading to the formation of highly unsaturated organo boronyl monomers (RBO), which could be easily identified because they cannot trimerize under single collision conditions. Besides the hydrogen displacement pathway, methylacetylene, dimethylacetylene, and propylene, carrying one or two methyl groups, were also found to eliminate a methyl group. In all systems, the reactions were barrierless, indirect, and initiated by addition of the boron monoxide radical to the π electron density of the hydrocarbon molecule, with the radical center located at the boron atom of the BO radical, thus leading to doublet radical intermediates. These intermediates either decompose via hydrogen or methyl loss or isomerize prior to their decomposition via atomic hydrogen or migration of the BO moiety. A consistent trend suggests that all exit transition states are rather tight with those involved in the hydrogen atom loss depicting exit barriers of typically 25 to 35 kJ mol, whereas the methyl loss pathways are associated with tighter exit transition states located about 30-50 kJ mol above the separated products. Further, the overall energetics suggest that those bimolecular reactions are exoergic by 40-90 kJ mol. These findings confirm that this reaction class leads to the formation of highly unsaturated organo boronyl molecules.

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“…For heavier chalcogens, the thioxoborane and selenoxborane with boron–sulfur and −selenium double bonds have been isolated by bulky ligands . In addition, higher bond order forms with BS entity in thioborine (HBS), halogenated sulfidoboron (XBS), and organo sulfidoboron (RBS) molecules as short-lived products of the high temperature gas-phase reactions. − However, there are barely examples reported for complexes containing aluminum or gallium with sulfur in multiple bonding characters.…”

Section: Introductionmentioning

confidence: 99%

M–S Multiple Bond in HMSH, H₂MS, and HMS Molecules (M = B, Al, Ga): Matrix Infrared Spectra and Theoretical Calculations

Zhao

Wang

et al. 2018

J. Phys. Chem. A

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Reaction products of B, Al, and Ga atoms with H2S have been identified in solid argon using matrix isolation infrared absorption spectroscopy. The results show that the ground state B atom reaction with H2S gives the H2BS molecule while for the Al atom the HAlSH molecule forms first, which then further isomerizes to H2AlS upon >500 nm irradiation. The reaction of the Ga atom with H2S only takes place upon photolysis to produce HGaSH in the matrix. The assignments of the major modes for these products were confirmed by appropriate 10B, 11B, D2S, and H2 34S isotopic shifts and theoretical frequency calculations. Topological analysis of the electron density suggests that both HBSH and H2BS molecules possess covalent B–S bond with significant double bond character, while the M–S bond in the heavier group 13 homologues (Al, Ga) was characterized as a polar covalent strong interaction.

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A combined crossed molecular beams and ab initio investigation on the formation of vinylsulfidoboron (C₂H₃¹¹B³²S)

Cited by 6 publications

References 55 publications

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X²Π) with Methylacetylene (CH₃CCH; X¹A₁) and D4-Methylacetylene (CD₃CCD; X¹A₁)

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X²Π) with Methylacetylene (CH₃CCH; X¹A₁) and D4-Methylacetylene (CD₃CCD; X¹A₁)

Exploring the Gas Phase Synthesis of the Elusive Class of Boronyls and the Mechanism of Boronyl Radical Reactions under Single Collision Conditions

M–S Multiple Bond in HMSH, H₂MS, and HMS Molecules (M = B, Al, Ga): Matrix Infrared Spectra and Theoretical Calculations

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A combined crossed molecular beams and ab initio investigation on the formation of vinylsulfidoboron (C2H311B32S)

Cited by 6 publications

References 55 publications

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X2Π) with Methylacetylene (CH3CCH; X1A1) and D4-Methylacetylene (CD3CCD; X1A1)

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X2Π) with Methylacetylene (CH3CCH; X1A1) and D4-Methylacetylene (CD3CCD; X1A1)

Exploring the Gas Phase Synthesis of the Elusive Class of Boronyls and the Mechanism of Boronyl Radical Reactions under Single Collision Conditions

M–S Multiple Bond in HMSH, H2MS, and HMS Molecules (M = B, Al, Ga): Matrix Infrared Spectra and Theoretical Calculations

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A combined crossed molecular beams and ab initio investigation on the formation of vinylsulfidoboron (C₂H₃¹¹B³²S)

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X²Π) with Methylacetylene (CH₃CCH; X¹A₁) and D4-Methylacetylene (CD₃CCD; X¹A₁)

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X²Π) with Methylacetylene (CH₃CCH; X¹A₁) and D4-Methylacetylene (CD₃CCD; X¹A₁)

M–S Multiple Bond in HMSH, H₂MS, and HMS Molecules (M = B, Al, Ga): Matrix Infrared Spectra and Theoretical Calculations