The molecular structure of seleno- and thiocarbonyl difluoride

Christen, Dines; Oberhammer, Heinz; Zeil, Werner; Haas, Alois; Darmadi, A.

doi:10.1016/0022-2860(80)80173-6

Cited by 39 publications

(4 citation statements)

References 18 publications

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“…Also, the CSe bond distances in 3a (1.816(6) Å) and 3b (1.789(6) and 1.798(6) Å) fall within the range of 1.608 to 2.021 Å (number reported 162, mean 1.857(4) Å) for CSe bonds found in the CSD database and the metal complexes of selenocarbonyl compounds but longer than those in selenoacetaldehyde (CH 3 C(H)Se; 1.758 Å, determined by microwave spectroscopy (MW)) and selenocarbonyl difluoride (F 2 CSe; 1.743 Å, measured by electron diffraction (ED)) . It is noteworthy that the CSe bond distances in 3b are very close to the value of 1.790 Å reported for the “pure” CSe bond in a selenoketone, 4,4‘-dimethoxyselenobenzophenone…”

Section: Resultsmentioning

confidence: 78%

Synthesis and Structure of Telluroamides and Selenoamides. The First Crystallographic Study of Telluroamides

Zingaro

Segi

et al. 1997

Organometallics

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The reaction between bis(trialkyltin) chalcogenides and trimethylaluminum results in the formation of bis(dimethylaluminum) chalcogenides, (Me2Al)2E, where E is S, Se, or Te. Reaction between the latter and carbonyl groups (but not carboxylic acids or esters) converts them to carbon−chalcogen double-bond (CE) compounds. Using this procedure, we have successfully synthesized several telluro- and selenocarbonyl compounds. The first successful synthesis of an isolable, crystalline telluroformamide, 4-(telluroformyl)morpholine (3c, C5H9NOTe), and its crystal structure are reported. Also, the syntheses and crystal structures of a γ-tellurolactam, 1-methyl-2-telluroxopyrroline (3d, C5H9NTe), and two selenoamides, N,N-diphenylselenoformamide (3a, C13H11NSe) and N-methyl-N-(4-nitrophenyl) selenoformamide (3b, C8H8N2O2Se) are described.

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Section: Resultsmentioning

confidence: 78%

Synthesis and Structure of Telluroamides and Selenoamides. The First Crystallographic Study of Telluroamides

Zingaro

Segi

et al. 1997

Organometallics

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“…The experimental information on the structures of selenocarbonyl compounds is very scarce, and we are only aware of that of selenoformaldehyde, selenocarbonyl difluoride, and selenoketene, while a partially resolved structure was reported for selenoacetaldehyde. The corresponding structural parameters are compared with our theoretical estimates in Table .…”

Section: Resultsmentioning

confidence: 99%

A Gas-Phase Basicity Scale for Selenocarbonyl Compounds Based on High-Levelab Initioand Density Functional Theory Calculations

1999

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A basicity scale for selenocarbonyl derivatives which covers a wide range of values (60 kcal/mol) has been established through the use of high-level ab initi o and DFT calculations. In our theoretical survey we have included selenoformaldehyde and the corresponding BH2, CH3, NH2, F, and Cl mono- and disubstituted derivatives, as well as carbonyl selenide, thiocarbonyl selenide, and selenoketene. With the only exception of selenoketene, which is a carbon base, all selenocarbonyl compounds investigated behave as selenium bases in the gas phase. Selenocarbonyl derivatives are predicted to be equally or slightly more basic than the thiocarbonyl analogues and, therefore, more basic than the corresponding carbonyl compounds. We have also shown, by means of G2-type calculations, that substituent effects on the relative stability of the neutral and the protonated forms of selenocarbonyl series are also rather similar to those estimated, at the same level of theory, for the thiocarbonyl series. For the neutrals these substituent effects are always stabilizing. Protonated species are strongly stabilized by σ- and π-electron donors, while they are destabilized by σ-withdrawing substituents. This explain the enhanced basicity of the methyl and amino derivatives and the low intrinsic basicity of the halogen derivatives. For the thiocarbonyl series the G2 calculated proton affinities are in very good agreement with the experimental values, which allow us to be confident in our estimates regarding the proton affinities of the selenocarbonyl derivatives investigated. The B3LYP/6-311+G(3df,2p) estimated proton affinities are slightly higher than the G2 values. The keto−enol isomerization of the methyl, hydroxy, and amino monosubstituted derivatives has been also studied.

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“…The C=S bond lengths are 1.618(3) Å ( 1 ) and 1.602(3) Å ( 2 ) indicating double bond character. They are the same in the 3 σ range for CSF 2 (1.589(3) Å [21] ) and CSCl 2 (1.604(5) Å [22] ) as derived from gas phase electron diffraction and microwave spectroscopy (see Table 1). The C−SCN bond lengths are in single bond range with 1.762(3) Å in 1 and 1.766(3) Å in 2 .…”

Section: Resultsmentioning

confidence: 73%

Thiocarbonyl Pseudohalides – The Curious Case of Thiocarbonyl Dithiocyanate

Pfeiffer,

Günther,

Fuzon

et al. 2024

Chemistry A European J

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Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn‐anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X‐ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kintetic reaction products by a lower transition stateas opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof‐ofprinciple study we show that it in turn can be used for the complexation of Ni2+ (4).

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The molecular structure of seleno- and thiocarbonyl difluoride

Cited by 39 publications

References 18 publications

Synthesis and Structure of Telluroamides and Selenoamides. The First Crystallographic Study of Telluroamides

Synthesis and Structure of Telluroamides and Selenoamides. The First Crystallographic Study of Telluroamides

A Gas-Phase Basicity Scale for Selenocarbonyl Compounds Based on High-Levelab Initioand Density Functional Theory Calculations

Thiocarbonyl Pseudohalides – The Curious Case of Thiocarbonyl Dithiocyanate

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