Carbonfluorine bond activation by iron(I). CF bond cleavage induced by addition of phosphines or thiols to a perfluorovinyldiiron complex

Rumin, René; Guennou, Karine; Pichon, R.; Pétillon, François Y.; Muir, Kenneth W.; Yufit, Dimitrii S.

doi:10.1016/s0022-328x(96)06844-1

Cited by 12 publications

(8 citation statements)

References 33 publications

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“…The resonances at δ 190.75 (d, 2 J CF = 9 Hz) and δ 49.3, which appeared as a split quartet due to the couplings 2 J C(C)F 3 = 37 Hz and 2 J C(C)F = 9 Hz, were respectively attributed to C α and C γ . The high-field resonance for the C α carbon atom differs greatly from that observed for the C α carbon atom (δ 225.2) in the closely related phosphino complex [{Fe(CO) 3 } 2 {μ-C α (F)C β (PPh 2 )C γ (CF 3 )SMe}],16b indicating that in 2 C α possesses only a small amount of carbene-like character relative to that observed in the phosphino complex. This was confirmed by the Fe(1)−C α bond length (1.998(4) Å) which is significantly longer than that in the phosphino compound (1.918(3) Å) 16b…”

Section: Resultsmentioning

confidence: 81%

“…The high-field resonance for the C α carbon atom differs greatly from that observed for the C α carbon atom (δ 225.2) in the closely related phosphino complex [{Fe(CO) 3 } 2 {μ-C α (F)C β (PPh 2 )C γ (CF 3 )SMe}],16b indicating that in 2 C α possesses only a small amount of carbene-like character relative to that observed in the phosphino complex. This was confirmed by the Fe(1)−C α bond length (1.998(4) Å) which is significantly longer than that in the phosphino compound (1.918(3) Å) 16b 1 View of a molecule of complex 2 , showing 20% probability ellipsoids for non-hydrogen atoms …”

Section: Resultsmentioning

confidence: 81%

“…When tetrafluoroethylene is coordinated to the bimetallic complex [Fe(CO) 3 (μ-SCH 3 )] 2 , it can be thermally transformed into a bridging C(F)CF 3 carbene by cleavage of a C−F bond and fluoride migration onto the electrophilic β-carbon atom of a σ−π-bonded vinyl group which is present in a dinuclear intermediate . The observation that the C−F bonds of ligands coordinated to mononuclear η 2 -vinyl molybdenum or tungsten complexes can be cleaved at room temperature to yield metal fluoride compounds 15 led us to investigate the behavior of the reactive perfluorovinyldiiron(I) cluster [{Fe(CO) 3 } 2 {μ-C(SMe)(CF 3 )CCF 2 }] ( 1 ) with nucleophiles such as thiols and secondary and tertiary phosphanes 16b PR 2 ,16b P(F)(OMe) 2 ,16a P(O)(OMe) 2 16a ) or of ionic species [(Ph 3 P)(CO) 2 Fe{μ-CFC(PPh 3 )C(CF 3 )(SMe)}Fe(CO) 3 ][{Fe(CO) 3 } 2 {μ-C(CF 3 )C(CF 3 )(SMe)}] 16a…”

Section: Introductionmentioning

confidence: 99%

“…The observation that the C−F bonds of ligands coordinated to mononuclear η 2 -vinyl molybdenum or tungsten complexes can be cleaved at room temperature to yield metal fluoride compounds 15 led us to investigate the behavior of the reactive perfluorovinyldiiron(I) cluster [{Fe(CO) 3 } 2 {μ-C(SMe)(CF 3 )CCF 2 }] ( 1 ) with nucleophiles such as thiols and secondary and tertiary phosphanes 16b PR 2 ,16b P(F)(OMe) 2 ,16a P(O)(OMe) 2 16a ) or of ionic species [(Ph 3 P)(CO) 2 Fe{μ-CFC(PPh 3 )C(CF 3 )(SMe)}Fe(CO) 3 ][{Fe(CO) 3 } 2 {μ-C(CF 3 )C(CF 3 )(SMe)}] 16a…”

Section: Introductionmentioning

confidence: 99%

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Carbon−Fluorine Bond Cleavages and Organoiron Ring Transformations: Reaction of a Perfluorosulfanylvinyldiiron(I) Complex with Amines

et al. 2000

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The reaction of the perfluorosulfanylvinyldiiron(I) complex [{Fe(CO) 3 } 2 {µ-C(SMe)(CF 3 )-C β (C R F 2 )}] (1) with secondary mono-and diamines (L ) Me 2 NH, (CH 2 ) 4 NH, HN(CH 2 ) 4 NH) in a 1:1 ratio in dichloromethane at room temperature led in a multistep reaction to the new monoaminocycloferrathiapentadiene compounds [{Fe(CO 5). However, when the reaction of 1 was conducted in THF with a large excess of amine, the diaminocycloferrathiabutene complexes [{Fe(CO) 3 } 2 {µ-S(Me)C(CF 3 )C(CX 2 )}] (X ) NMe 2 (6), N(CH 2 ) 4 ( 7)) and [{Fe(CO) 3 } 2 {µ-S(Me)C(CF 3 )C(CX)}] (X ) MeN(CH 2 ) 2 NMe (8), HN(CH 2 ) 2 NH (9)) were formed. It is suggested that these compounds form via initial nucleophilic attack at C R to give the common zwitterionic intermediate [{Fe(CO) 3 } 2 {µ-S(Me)C-(CF 3 )C(CFNX 2 )] (C). Thermally induced C-F bond activation is a feature of these reactions. Thermolysis of diaminocycloferrathiabutene compounds (6-9) in tetrahydrofuran gave the amidinium-substituted µ | -alkyne derivatives [{Fe(CO) 3 } 2 (µ-SMe){µ-(CF 3 )CdC(CX 2 )}] (X ) NMe 2 (10), N(CH 2 ) 4 ( 11)) and [{Fe(CO) 3 } 2 (µ-SMe){µ-(CF 3 )CdC(CX)}] (X ) MeN(CH 2 ) 2 NMe (12), NH(CH 2 ) 2 NH ( 13)), in quantitative yields via C-S bond scission. The molecular structures of 6, 8, and 10 have been established by X-ray diffraction studies.

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Section: Resultsmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Carbon−Fluorine Bond Cleavages and Organoiron Ring Transformations: Reaction of a Perfluorosulfanylvinyldiiron(I) Complex with Amines

et al. 2000

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“…2 For example, we have shown that the C᎐F bonds in perfluorosulfanylvinyliron(I) complexes can be activated under mild conditions by primary and secondary amines, by thiols and by secondary phosphines PH(X)Y to give molecular complexes containing cycloferrathiapentadiene rings. 3,4 We have extended these investigations, using tertiary phosphanes as the nucleophilic reagent, and now report reactions between the perfluorosulfanylvinyldiiron cluster…”

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confidence: 99%

Carbon–fluorine activation by iron(I): organoiron ring transformation promoted by addition of tertiary phosphanes to a perfluorosulfanylvinyldiiron(I) complex

Rumin¹,

Guennou²,

Pétillon³

et al. 1997

J. Chem. Soc., Dalton Trans.

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Activation and Functionalization of Vinylic C−F Bonds by Transition Metal Compounds: The Factors Determining Reactions between Nucleophiles and a (Perfluorovinyl)diiron(I) Complex; Syntheses of Diiron Derivatives Containing New C−N, C−S, C−H and C−O Bonds

Cadenet

Rumin

Pétillon

et al. 2002

Eur. J. Inorg. Chem.

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The reactions between alcohols ROH (R = Me, Et) and RR(OH)2 (RR = CH2−CH2) and the [perfluoro(sulfanyl)vinyl]diiron complex [{Fe(CO)3}2{µ‐C(SMe)(CF3)CβCαF2}] (1) in THF at room temperature involve substitution at the Cα atom to give new (alkoxymethylene)thiaferracyclobutadiene compounds [{Fe(CO)3}2{µ‐S(Me)C(CF3)CβCα(OR)2}] [R = Me (2a), Et (2b); RR = CH2CH2 (2c)]. Treatment of 1 with aniline and (methoxycarbonyl)hydrazine, bases of intermediate strength according to Pearson, produces α,β‐substituted thiaferracyclopentadiene [{Fe(CO)3}2{µ‐S(Me)C(CF3)Cβ(NHR)Cα(NHR)}] [R = Ph (5a), NHC(O)OMe (5b)] complexes. It is suggested that these compounds form through initial nucleophilic attack at Cα to give the zwitterionic intermediate [{Fe(CO)3}2{µ‐S(Me)C(CF3)CC(NRH)2}] (f). Thermally induced C−F bond activation is a feature of these reactions. When 1 reacts with thioamides containing three “hard” competitive primary and secondary amine functions and one “soft” thione function, the nucleophile first attacks at Cα through a secondary amine and, in a second step, at Cβ through the thiol function to give α,β adducts [{Fe(CO)3}2{µ‐S(Me)C(CF3)CβSC(=NR2)N(R1)Cα(Cβ−Cα)] [R1 = NH2, R2 = CH3 (6a); R1 = CH3, R2 = H (6b); R1 = R2 = CH3 (6c)] possessing novel iminothiazolidine systems fused to the five‐membered metallacyclic ring. Treatment of 1 with acetylhydrazine, which has three “hard” nucleophilic functions, results in the formation of the compound [{Fe(CO)3}2{µ‐S(Me)C(CF3)C(H)C(10)NNC(Me)O(C(10)−O)}] (7a), in which an oxadiazole function is fused to the thiaazaferracyclohexene ring. The position of the fluorine substituent on the CαCβCγ(CF3)S(Me) ring of ferracyclopentadiene complexes has been found to be the essential factor determining the specific activation of the C−F bond. A single fluoro substituent attached to the β‐carbon atom of the chain can be activated by nucleophiles to give α,β adducts [{Fe(CO)3}2{µ‐S(Me)C(CF3)Cβ(X)Cα(NRR′)}] [X = OR′′, R = R′ = R′′ = Me (3a); X = OR′′, R = R′′ = Me, R′′ = C(O)NMe2 (3b); X = SR′′ (4)]. In contrast, complexes in which a single fluorine atom is linked to the α‐carbon atom do not undergo C−F bond cleavage reactions. X‐ray structures of compounds 2a, 3b, 5a, 5b, 6a and 7a are reported.

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Carbonfluorine bond activation by iron(I). CF bond cleavage induced by addition of phosphines or thiols to a perfluorovinyldiiron complex

Cited by 12 publications

References 33 publications

Carbon−Fluorine Bond Cleavages and Organoiron Ring Transformations: Reaction of a Perfluorosulfanylvinyldiiron(I) Complex with Amines

Carbon−Fluorine Bond Cleavages and Organoiron Ring Transformations: Reaction of a Perfluorosulfanylvinyldiiron(I) Complex with Amines

Carbon–fluorine activation by iron(I): organoiron ring transformation promoted by addition of tertiary phosphanes to a perfluorosulfanylvinyldiiron(I) complex

Activation and Functionalization of Vinylic C−F Bonds by Transition Metal Compounds: The Factors Determining Reactions between Nucleophiles and a (Perfluorovinyl)diiron(I) Complex; Syntheses of Diiron Derivatives Containing New C−N, C−S, C−H and C−O Bonds

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