The crystal and molecular structures of the thiobenzophenone S-oxide and thiobenzophenone

Rindorf, G.; Carlsen, Lars

doi:10.1107/s0567740879005835

Cited by 40 publications

(17 citation statements)

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“…The sulfide and isocyano groups occupy trans positions around the rhodium centre, suggesting that C−S bond cleavage liberates isocyanide, which later coordinates on the opposite side of the metal, or that after C−S bond cleavage, the isocyanide and triphenylphosphine ligands are able to exchange positions to achieve a more stable configuration. The C−S bond distance of 1.775(8) Å in the pincer central anchor point is significantly elongated from the C−S bond distance in thiobenzophenone, and comparable to distances in previously reported zerovalent group 10 η 2 ‐thiobenzophenone complexes {range from 1.769(2) Å (Ni 0 ) to 1.815(11) Å (Pt 0 )}. 9 The sum of the bond angles around the central pincer carbon (C1), excluding bonds to the rhodium centre {equal to 347(1)°}, deviates greatly from 360°, indicative of loss of sp 2 character, as expected in the case of a thiirane.…”

Section: Methodssupporting

confidence: 86%

C−N, C−S and S−S Bond Cleavage by Rhodium PC_carbeneP Pincer Complexes

Tinnermann

Young

2020

Chemistry An Asian Journal

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Rhodium PCcarbeneP complexes 1‐L {L=PPh3, PPh2(C6F5)} react with isothiocyanate, carbodiimide and disulphide to enable C−S, C−N and S−S bond cleavage. The cleaved molecules are sequestered by the metal center and the pincer alkylidene linkage, forming η2‐coordinated sulfide or imide centered pincer complexes. When a C−S or S−S bond is cleaved, the resulting complexes can bridge two rhodium centers through sulphur forming dimeric complexes and eliminating a monodentate phosphine ligand.

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Section: Methodssupporting

confidence: 86%

C−N, C−S and S−S Bond Cleavage by Rhodium PC_carbeneP Pincer Complexes

Tinnermann

Young

2020

Chemistry An Asian Journal

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“…In this structure (refcode: JEPVIJ [48] ), thioketone 5 acts as a ligand to Cr(CO) 4 the Fc substituent are rotated by 18.1 , which points to its in-between conformation, neither eclipsed nor staggered. The τ Ph value of 5 is very close to one of the τ Ph angles measured for the crystal structure of diphenyl thioketone (τ Ph = 317.4 and 328.1 ; refcode: THBZPS10 [49] ). The structures with refcodes JEPVIJ and BEHGAW [50] suggest that the Cp ring bonded to the C S group tends to be rotated only slightly, while the Ph substituent can be tilted by as much as 83.4 if the thiocarbonyl sulfur is complexed with a metal.…”

Section: Resultssupporting

confidence: 72%

Ferrocenyl hetaryl thioketones: A computational study of their conformational stability

Matczak

Mlostoń

Weigand

2019

Int J of Quantum Chemistry

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In this work, the conformational behavior of ferrocenyl‐ and hetaryl‐functionalized thioketones was studied by means of computational quantum chemical methods. Four hetaryl substituents (furan‐2‐yl, thiophen‐2‐yl, selenophen‐2‐yl, and N‐methylpyrrol‐2‐yl) were taken into account. The conformational space of the four ferrocenyl hetaryl thioketones was explored, and all found conformers were characterized using density functional (B3LYP) and wave function (SCS‐MP2) theories. Their stability was explained in terms of intramolecular interactions. Such interactions were described using the methods of natural bond orbitals, “atoms in molecules,” noncovalent interaction index, and localized molecular orbital energy decomposition analysis. The identified conformations essentially differ in the arrangement of hetaryl heteroatom relative to the thiocarbonyl sulfur atom. The furan‐2‐yl substituent favors an s‐trans‐like arrangement of its heteroatom, while the remaining hetaryl substituents tend to adopt an s‐cis‐like arrangement. Such a conformational preference mainly results from the π → π* stabilization between the CS group and the hetaryl ring. Weak intramolecular hydrogen bonding of CH⋯O type was detected in the preferred conformer of ferrocenyl furan‐2‐yl thioketone. Low‐polarity solvents, such as toluene, chloroform, and tetrahydrofuran, have a small effect on the preferred conformers of the four thioketones.

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“…For the thiocyanate bond with the phosphorous atom in PTCCP, the P-S and S-C bond lengths were 2.23 and 1.68 Å, respectively. These values are in agreement with the values reported by Okuniewski et al for the P-S bond 27 and Rindorf et al and Kenneth et al for the S-C bond [28][29] . The P-C bond length in PTCCP was 1.82 Å; and this value was reported to be 1.92 and 1.81 Å by Athanassios et al and Priya et al, respectively [30][31] .…”

Section: Structural Properties Of the Molecular Geometrysupporting

confidence: 83%

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

Lashgari

Ghamami

Salgado-Morán

et al. 2016

J. Chil. Chem. Soc.

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Two new phosphorus complexes, potassium trichlorothiocyanophosphate (III) (PTCTCP; K[PCl 3 (SCN)]) and potassium trichlorocyanophosphate (III) (PTCCP; K[PCl 3 (CN)]) were synthesized from the reaction of KSCN and KCN, respectively, with PCl 3 . The chemical formulas and compositions of these compounds were determined by elemental analysis and spectroscopic methods, such as phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy ( 31 P-NMR), Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy and mass spectrophotometry. All of the theoretical calculations and determinations of the properties of these compounds were performed as part of the Amsterdam Density Functional (ADF) program. Excitation energies were assessed using time-dependent perturbation density functional theory (TD-DFT). In addition, the molecular geometry was optimized and the frequencies and excitation energies were calculated using standard Slater-type orbital (STO) basis sets with triple-zeta quality double plus polarization functions (TZ2P) for all of the atoms. The assignment of the principal transitions and total densities of state (TDOS) for orbital analysis were performed using the GaussSum 2.2 program.

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The crystal and molecular structures of the thiobenzophenone S-oxide and thiobenzophenone

Abstract: The crystal and molecular structures of thiobenzophenone S-oxide, C~aHt0OS (TBPSO), and thiobenzophenone, CtaH~0S (TBP), were determined from diffractometer data. The unit cell of TBPSO is orthorhombic, space group P2~2~21; a = 5.903 (3)

Cited by 40 publications

References 2 publications

C−N, C−S and S−S Bond Cleavage by Rhodium PC_carbeneP Pincer Complexes

C−N, C−S and S−S Bond Cleavage by Rhodium PC_carbeneP Pincer Complexes

Ferrocenyl hetaryl thioketones: A computational study of their conformational stability

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

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The crystal and molecular structures of the thiobenzophenone S-oxide and thiobenzophenone

Abstract: The crystal and molecular structures of thiobenzophenone S-oxide, C~aHt0OS (TBPSO), and thiobenzophenone, CtaH~0S (TBP), were determined from diffractometer data. The unit cell of TBPSO is orthorhombic, space group P2~2~21; a = 5.903 (3)

Cited by 40 publications

References 2 publications

C−N, C−S and S−S Bond Cleavage by Rhodium PCcarbeneP Pincer Complexes

C−N, C−S and S−S Bond Cleavage by Rhodium PCcarbeneP Pincer Complexes

Ferrocenyl hetaryl thioketones: A computational study of their conformational stability

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

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C−N, C−S and S−S Bond Cleavage by Rhodium PC_carbeneP Pincer Complexes

C−N, C−S and S−S Bond Cleavage by Rhodium PC_carbeneP Pincer Complexes