Die Koordinationscheme CS-funktioneller verbindungen

Schenk, Wolfdieter A.; Rüb, Doris; Burschka, Christian

doi:10.1016/0022-328x(87)80246-2

Cited by 14 publications

(2 citation statements)

References 69 publications

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“…Consistent with this, the S1-C7 bond of 1.7857(18) Å is of single bond and slightly shorter than the S2-C7 bond (1.796(2) Å). However, the related values of 4-t BuC 6 H 4 C(@S)SMe are 1.630 (C@S), 1.724 (C-SMe) and 1.788 (S-Me) Å [42]. Thus, the C7 atom in 1 is sp 3 -hybridized, this fact is in agreement with the below-described 13 C NMR spectroscopy.…”

Section: X-ray Structures Of Complexessupporting

confidence: 88%

Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G=Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

Shi

Cheng

et al. 2013

Polyhedron

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Section: X-ray Structures Of Complexessupporting

confidence: 88%

Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G=Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

Shi

Cheng

et al. 2013

Polyhedron

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“…))] 25 -we looked for appropriate ways to modify reagent 1. Indeed, the lability of CO ligands on 1 and their facile exchange for tertiary phosphines has been noted on several occasions, 26,27 and accordingly the reaction with the bidentate donor dmpe proceeded in excellent yield.…”

Section: Discussionmentioning

confidence: 99%

Synthesis, structure, DFT calculations, and full vibrational analysis of the prototypical thioformaldehyde complex mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(η²-SCH₂)]

Schenk

Vedder

Klüglein

et al. 2002

J. Chem. Soc., Dalton Trans.

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Thiono, Selenothiono, and Dithiocarboxylic Ester Complexes from Pentacarbonyl(thiobenzaldehyde)tungsten and π‐Donor Substituted Alkynes and Decomplexation of the Esters

1995

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Pentacarbonyltungsten-coordinatedthiobenzaldehyde, [(CO),W(S=C(Ph)HJ] ( l ) , reacts with l-methylthio-l-propyne, 1-ethylseleno-1-propyne, and alkoxyethynes by insertion of the C=C into the S=C bond to form in a highly regioand stereoselective manner the a,P-unsaturated dithio, selenothiono, and thionocarboxylic ester complexes (E)(C=C)- Complex 3c has been characterized by an X-ray structural analysis.Simple thioaldehydes such as e.g. thioacetaldehyde and thiobenzaldehyde are unstable compounds and immediately oligomerize [I]. This considerably restricts their potential use in organic synthesis. Thioaldehydes can be stabilized in several ways: by bulky substituents, x-donor groups at the thiocarbonyl carbon or by coordination to a transition metal.The problems connected with the high reactivity of thioaldehydes can be circumvented by using their complexes. In recent years, pentacarbonylchromium-, -molybdenum-, and -tungsten-coordinated thio-and selenoaldehydes and -ketones turned out to be conveniently accessible C=S and C=Se building blocks for the synthesis of S-and Se-containing Diels-Alder reactions with conjugated dienes gave e.g. 6-membered heterocycles and thia-and selenanorbornene derivatives, respecti~ely [~]. Cycloadditions with vinyl ethers afforded thietane and selenetane complexes [4]. By ring enlargement these 4-membered heterocycles can subsequently be transformed into 5-and 6-membered containing two heteroatoms. Thiirane derivatives and their complexes are obtained from pentacarbonyl(thiobenza1dehyde)tungsten and diphenyldiaz~methane [~].We also observed that the C=C bonds of l-diethylamino-1-propyne and bis(diethy1amino)ethyne insert into the X=C bond of [(CO),M{X=C(Aryl)R}] (M = Cr, W; X = S, Se, 're; R = H, Aryl) to form transition metal-bound thio-, seleno-, and telluroacrylamide derivative^ [^^^]. Decomplexation of these ligands yields the free heterobutadiene derivativesrs1. An extension of this route to other n-donorsubstituted alkynes offers -in principle -an easy access to a series of different a,P-unsaturated thione-and selenone derivatives. In this paper we report on the synthesis of thiono, selenothiono, and dithiocarboxylic ester complexes and on the decomplexation of representative examples. Results and DiscussionAnalogously to the reaction of pentacarbonylthio-and -selenobenzaldehyde chromium and tungsten with 1 -diethylamino-1-propyne, complex 1 reacts with l-methylthio-1-(2a) and 1-ethylseleno-1-propyne (2b) by formal insertion of the C=C bond into the S=C bond. After chromatography the dithio-and the selenothionocarboxylic ester complexes 3a and 3b, respectively, were obtained in moderate yields (Scheme 1). Scheme 1 3a-dThe reaction very likely proceeds by cycloaddition of the C=C bond of the alkyne to the S=C bond of 1 to form a thiete complex. Subsequent electrocyclic ringopening gives the final products 3a and 3b. Since it has neither been possible to isolate nor to spectroscopically detect the thiete complex, ring opening must be rapid compared to cycloaddition. Thiete forma...

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Die Koordinationscheme CS-funktioneller verbindungen

Cited by 14 publications

References 69 publications

Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G=Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G=Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

Synthesis, structure, DFT calculations, and full vibrational analysis of the prototypical thioformaldehyde complex mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(η²-SCH₂)]

Thiono, Selenothiono, and Dithiocarboxylic Ester Complexes from Pentacarbonyl(thiobenzaldehyde)tungsten and π‐Donor Substituted Alkynes and Decomplexation of the Esters

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Die Koordinationscheme CS-funktioneller verbindungen

Cited by 14 publications

References 69 publications

Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G=Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G=Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

Synthesis, structure, DFT calculations, and full vibrational analysis of the prototypical thioformaldehyde complex mer-[W(CO)3(Me2PC2H4PMe2)(η2-SCH2)]

Thiono, Selenothiono, and Dithiocarboxylic Ester Complexes from Pentacarbonyl(thiobenzaldehyde)tungsten and π‐Donor Substituted Alkynes and Decomplexation of the Esters

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Synthesis, structure, DFT calculations, and full vibrational analysis of the prototypical thioformaldehyde complex mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(η²-SCH₂)]