Reactions of the thiocarbene complex Cp(CO)2Fe[CH(SMe)]+ with nucleophiles

Yu, Yeung S.; Angelici, Robert J.

doi:10.1021/om50002a014

Cited by 17 publications

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“…After 48 h, this transformation process is nearly complete. In the 1 H NMR spectrum, a set of distinct signals were observed at δ 5.45, corresponding to the protons of the vinylthioether unit, η 3 -CH 2 =C H SAr …”

Section: Resultsmentioning

confidence: 99%

“…In the 1 H NMR spectrum, a set of distinct signals were observed at δ 5.45, corresponding to the protons of the vinylthioether unit, η 3 -CH 2 =CHSAr. 49 The solid-state structure of [4] Acetylide and Vinyl Complexes. Although deprotonation of cationic vinylidene complexes has been reported to yield the alkynyl complexes, 30,50 compound 2 remains stable toward common bases such as pyridine and NEt 3 .…”

Section: ■ Introductionmentioning

confidence: 99%

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Transformation of Acetylene to Ethenylidene, Carbene, Acetylide, Vinyl, and Olefin Groups with Cp*Fe(1,2-Cy₂PC₆H₄S)

Zhang,

Feng,

Tung

et al. 2023

Inorg. Chem.

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Tautomerization of C 2 H 2 at half-sandwich compound Cp*Fe-(1,2-Cy 2 PC 6 H 4 S) exclusively produces an iron ethenylidene, Cp*Fe-(=C=CH 2 )(1,2-Cy 2 PC 6 H 4 S) (2). Protonation of the ethenylidene causes nucleophilic attack of the C α by sulfur, affording a sulfur-tethered carbene complex, [Cp*Fe=C(CH 3 )SC 6 H 4 PCy 2 ] + (3 +). This Fischer-type carbene complex undergoes an unusual isomerization by migrating a hydrogen atom from the β-CH 3 group to the α-C, leading to the formation of an olefin complex [Cp*Fe(η 4 -CH=CH 2 SC 6 H 4 PCy 2 ] + (4 + ). Compound 2 also displays diverse redox reactivities. It transforms to a neutral acetylide ferric complex (5) when reacting with free radical scavengers and to a cationic vinyl complex [Cp*Fe(η 3 -C(=CH 2 )SC 6 H 4 PCy 2 ] + (6 + ) upon 1e − oxidation. The interconversion between the vinyl and acetylide complexes can be realized through protonation/ deprotonation reactions.

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Section: Resultsmentioning

confidence: 99%