Iron complexes of thioacroleins derived from thietes

Takahashi, K.; Iwanami, Masaru; Tsai, Ah‐Lim; Chang, Peter L.; Harlow, Richard L.; Harris, L. E.; McCaskie, John E.; Pfluger, C. E.; Dittmer, Donald C.

doi:10.1021/ja00799a046

Cited by 20 publications

(4 citation statements)

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“…In addition, elemental analysis indicated the presence of a mononuclear iron complex with the molecular formula C 17 H 13 Fe 2 O 3 S. Finally, single X-ray structure analysis confirmed the formation of the η 4 -1-thia-1,3-diene-type tricarbonyl iron complex 2 (Figure 1). Prior to this work, similar complexes have been found in reactions of 1,3-thiete with Fe 2 (CO) 9 [15] as well as some 1-thia-1,3-dienes with iron carbonyls, i. e. α,β-unsaturated thioamides and thioesters with Fe 2 (CO) 9 [16] and thiochalcones with Fe 3 (CO) 12 . [14] Very recently, a detailed theoretical study on both σ-type FeÀ S and FeÀ C bonds in complexes of the latter type was reported by our group.…”

Section: Synthesis and Characterizationsupporting

confidence: 70%

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe₃(CO)₁₂

et al. 2022

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Dedicated to Prof. Jozef Drabowicz on the occasion of his 75th birthday.In continuation of the study focused on synthesis and structure of mimics of the active site of the [FeFe] hydrogenase enzyme, reaction of Fe 3 (CO) 12 with cyclopropyl ferrocenyl thioketone 1 was carried out. Two different complexes with ring-opened cyclopropyl fragments were isolated and identified as η 4 -1-thia-1,3-diene-type mononuclear tricarbonyl iron complex 2 and η 2acyl-type hexacarbonyl diiron complex 3, respectively. Struc-tures of crystalline products were unambiguously confirmed by single crystal X-ray analysis. For the ring opening reaction of the cyclopropane moiety, leading to the formation of 2 and 3, a multistep radical mechanism was postulated. Electrochemical investigations of 3, being reminiscent of a [FeFe] hydrogenase mimic, were carried out at different scan rates.

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Section: Synthesis and Characterizationsupporting

confidence: 70%

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe₃(CO)₁₂

et al. 2022

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“…[6] While this as expected attenuates their otherwise high reactivity, the coordinated C=S group is still susceptible to a range of nucleophilic addition and cycloaddition reactions. [15] Surprisingly, there are only a few examples of complexes of a,b-unsaturated thioaldehydes with the metals tungsten, [16][17][18] iron, [19,20] cobalt, [19][20][21] and iridium. [22] Abstract: Ruthenium hydrogensulfido complexes [CpRuA C H T U N G T R E N N U N G (P À P)(SH)] ((P À P)= Ph 2 PCH 2 PPh 2 (dppm), Ph 2 PC 2 H 4 PPh 2 (dppe)) were obtained from the corresponding chloro complexes by Cl/SH exchange.…”

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confidence: 99%

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

Schenk

Beucke

Burzlaff

et al. 2006

Chemistry A European J

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Ruthenium hydrogensulfido complexes [CpRu(P-P)(SH)] ((P-P)=Ph(2)PCH(2)PPh(2) (dppm), Ph(2)PC(2)H(4)PPh(2) (dppe)) were obtained from the corresponding chloro complexes by Cl/SH exchange. Condensation with a range of cinnamaldehydes gave thiocinnamaldehyde complexes [CpRu(P-P)(S=CH-CR(2)=CHR(1))]PF(6) (R(1)=C(6)H(4)X, R(2)=H, Me, X=H, OMe, NMe(2), Cl, NO(2)) as highly-colored crystalline compounds. The thiocinnamaldehyde complexes undergo [4+2]-cycloaddition reactions with vinyl ethers CH(2)=CHOR(3) (R(3)=Et, Bu) and styrenes H(2)C=CHC(6)H(4)Y (Y=H, Me, OMe, Cl, Br, NO(2)) to give complexes of 2,4,5-trisubstituted 3,4-dihydro-2H-thiopyrans as mixtures of two diastereoisomers. The rate of addition of para-substituted styrenes H(2)C=CHC(6)H(4)Y to [CpRu(dppm)(S=CH-CH=CHPh)]PF(6) increases in the series Y=NO(2), Br, Cl, H, Me, OMe, indicating that the cycloaddition is dominated by the HOMO(dienophile)-LUMO(diene) interaction. The strained dienophiles norbornadiene and norbornene also add, giving ruthenium complexes of 3-thia-tricyclo[6.2.1.0(2,7)]undeca-4,9-dienes and 3-thia-tricyclo[6.2.1.0(2,7)]undec-4-enes, respectively. Addition reactions with acrolein, methacrolein, methyl vinyl ketone, acrylic ester, or ethyl propiolate finally yielded ruthenium complexes of 3,4-disubstituted 3,4-dihydro-2H-thiopyrans and 4H-thiopyrans, respectively.

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“…In contrast to their oxygen analogues, thiocarbonyl co~npounds have been co~nparatively little studied.' One important reason for this lies in their impressive tendency to oligo-or polymerize, 21 property which results in several chenlically intelligent potential routes to thiones leading to intractable or undesirable products. Although Inany difficulties have been overconle (sinlple aliphatic thiones have, for instance, recently been isolated free from enethiol(4)), paths to the Inore reactive thiones and to thials in 1110110meric forill, are lacking.…”

mentioning

confidence: 99%

“…he infrared spectra of thernlolysates con-4An inorganic complex of thioacrolein has been isolated recently (21).…”

mentioning

confidence: 99%

The flash thermolysis of allyl sulphides

Giles¹,

Marty²,

Mayo³

1976

Can. J. Chem.

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Iron complexes of thioacroleins derived from thietes

Cited by 20 publications

References 1 publication

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe₃(CO)₁₂

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe₃(CO)₁₂

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

The flash thermolysis of allyl sulphides

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Iron complexes of thioacroleins derived from thietes

Cited by 20 publications

References 1 publication

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe3(CO)12

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe3(CO)12

Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]‐Cycloaddition Reactions

The flash thermolysis of allyl sulphides

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A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe₃(CO)₁₂

A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe₃(CO)₁₂