Metallocenic thioketones as two-electron ligands

Andrianov, V. G.; Struchkov, Yu. T.; Petrovskii, P. V.; Fedin, É. I.; Kursanov, D. N.; Dolgova, S. P.; Setkina, V. N.

doi:10.1016/s0022-328x(00)89053-1

Cited by 20 publications

(4 citation statements)

References 3 publications

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“…However, the aqua ligand is replaced by acetone oxime to yield [Os 1 {C 6 H 4 (O 1 )CH 3 }(η 2 ‐H 2 ){N(OH)=C(CH 3 ) 2 }(P i Pr 3 )( Os 1 –O 1 )][BF 4 ] derivative. The methyl dithioformate binds to the metal atom through the lone pair of electrons present on the sulfur atom as in thioethers28 and thioureas 29. The bonding of the alkyl dithioformate to the metal atom will be discussed in detail in the latter part of this article.…”

Section: Resultsmentioning

confidence: 98%

“…Fairlie et al29 showed that thiourea in [(NH 3 ) 5 Ru{SC(NH 2 ) 2 }](S 2 O 6 ) 3/2 · H 2 O is a good π‐donor ligand. Setkina and co‐workers28 reported that the thiobenzylcyclopentadienyl ligand in [(η 5 ‐C 5 H 5 )(CO) 2 Mn←S=C(Ph)(C 5 H 4 )Mn(CO) 3 ] complexes shows both acceptor and donor properties. Hence the alkyl dithioformate/dithioformic acid bound to the metal atom is presumed to be a good π‐acceptor and π‐donor ligand.…”

Section: Resultsmentioning

confidence: 99%

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Simplified process for the production of sesame protein concentrate. Differential scanning calorimetry and nutritional, physicochemical and functional properties

et al. 2003

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The effects of a simplified production process on the yield, protein content and differential scanning calorimetric analysis of a sesame protein concentrate were studied. The results were compared with those for similar products obtained by the traditional method. The protein content of the (spraydried) sesame concentrate obtained by the simplified process (549 g kg −1 ) was similar to that of the concentrates obtained by the traditional method (515-565 g kg −1 ). Spray-dried samples showed higher T d and T m and lower H than freeze-dried samples. In addition, the chemical composition, nutritional quality and physicochemical and functional characteristics of the sesame protein concentrate obtained by the simplified process were compared with those of a similar soybean product. The protein, lysine and calcium contents of the sesame concentrate were lower than those of the soybean concentrate, but the digestibility of the protein was the same for both products. The phytic acid content of the sesame concentrate diminished significantly, but was still higher than that of the soybean concentrate. The water absorption and protein solubility were higher for the soybean concentrate, whereas the oil absorption and viscosity at pH 3 were higher for the sesame concentrate.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Simplified process for the production of sesame protein concentrate. Differential scanning calorimetry and nutritional, physicochemical and functional properties

et al. 2003

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“…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). The structures with refcodes JEPVIJ and BEHGAW 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. A search through the CSD for Fc‐functionalized thioketones yielded 15 crystal structures (Table S2) and the overwhelming majority of the structures possess their Fc substituent in nearly eclipsed conformations.…”

Section: Resultsmentioning

confidence: 99%

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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“…Coordination of 1,2-diacylcyclopentadienyl to [Mn(CO) 3 ] is accomplished by deprotonation of 1a − h with thallium(I) ethoxide in THF to give thallium reagents 4a − h , followed by reaction with [MnBr(CO) 5 ] to give diacyl complexes [Mn{η 5 -1,2-C 5 H 3 (COR) 2 }(CO) 3 ] ( 5a − h ) in high yield. Reactions of 5a − h with Lawesson's reagent do not cleanly close the acyl groups to thiophenes, but the method used by Kursanov , to convert monoacyl cymantrenes to thiones works well. Reactions of [Mn{η 5 -1,2-C 5 H 3 (COR) 2 }(CO) 3 ] ( 5c − e , h ) with P 4 S 10 /NaHCO 3 in refluxing CS 2 give [Mn(η 5 -SC 7 H 3 -1,3-R 2 )(CO) 3 ] ( 3c , 35%; 3d , 33%; 3e , 21%; 3h , 33%).…”

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confidence: 99%

Synthesis, Characterization, and Structure of Cyclopenta[c]thiophenes and Their Manganese Complexes

et al. 2005

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1,3-Diaryl-4H-cyclopenta[c]thiophenes are efficiently prepared from 1,2-diaroylcyclopentadienes by use of Lawesson's reagent. eta5-Cyclopenta[c]thienyl complexes, [Mn(eta5-SC7H3-1,3-R2)(CO)3] (R = Me, Ph), are prepared in high yield by ligand substitution reactions of [MnBr(CO)5] with [SnMe3(SC7H3-1,3-R2)]. Alternatively, thiation with P4S10/NaHCO3 converts [Mn{eta5-1,2-C5H3(COR)2)(CO)3] to [Mn(eta5-SC7H3-1,3-R2)(CO)3] (R = Ph, 4-tolyl, 4-MeOC6H4, benzo[2,3-b]thienyl). The molecular structures of complexes with R = Me, Ph show planar eta5-cyclopenta[c]thienyl ligands, with the manganese atom slightly displaced away from the ring-fusion bond.

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Metallocenic thioketones as two-electron ligands

Cited by 20 publications

References 3 publications

Simplified process for the production of sesame protein concentrate. Differential scanning calorimetry and nutritional, physicochemical and functional properties

Simplified process for the production of sesame protein concentrate. Differential scanning calorimetry and nutritional, physicochemical and functional properties

Ferrocenyl hetaryl thioketones: A computational study of their conformational stability

Synthesis, Characterization, and Structure of Cyclopenta[c]thiophenes and Their Manganese Complexes

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