Über den photochemischen und oxydativen Abbau von Carbonylen

Reihlen, Hans; Gruhl, A.; Heßling, G. v.

doi:10.1002/jlac.19294720113

Cited by 53 publications

(26 citation statements)

References 7 publications

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“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] The sub-site resembles wellstudied organometallic Fe I Fe I complexes of the type [(m-RS) 2 Fe 2 (CO) 6 ] (R= bridging organic group) [22,23] and such complexes provide precursors to di-cyanide derivatives such as [Fe 2 (CO) 4 (CN) 2 {CH 2 (CH 2 S) 2 …”

Section: }]mentioning

confidence: 99%

Dissecting the Intimate Mechanism of Cyanation of {2Fe3S} Complexes Related to the Active Site of All‐Iron Hydrogenases by DFT Analysis of Energetics, Transition States, Intermediates and Products in the Carbonyl Substitution Pathway

Zampella¹,

Bruschi²,

Fantucci³

et al. 2004

Chemistry A European J

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A bridging carbonyl intermediate with key structural elements of the diiron sub-site of all-iron hydrogenase has been experimentally observed in the CN/CO substitution pathway of the {2Fe3S} carbonyl precursor, [Fe(2)(CO)(5){MeSCH(2)C(Me)(CH(2)S)(2)}]. Herein we have used density functional theory (DFT) to dissect the overall substitution pathway in terms of the energetics and the structures of transition states, intermediates and products. We show that the formation of bridging CO transitions states is explicitly involved in the intimate mechanism of dicyanation. The enhanced rate of monocyanation of {2Fe3S} over the {2Fe2S} species [Fe(2)(CO)(6){CH(2)(CH(2)S)(2)}] is found to rest with the ability of the thioether ligand to both stabilise a mu-CO transition state and act as a good leaving group. In contrast, the second cyanation step of the {2Fe3S} species is kinetically slower than for the {2Fe2S} monocyanide because the Fe2 atom is deactivated by coordination of the electron-donating thioether group. In addition, hindered rotation and the reaction coordinate of the approaching CN(-) group, are other factors which explain reactivity differences in {2Fe2S} and {2Fe3S} systems. The intermediate species formed in the second cyanation step of {2Fe3S} species is a mu-CO species, confirming the structural assignment made on the basis of FT-IR data (S. J. George, Z. Cui, M. Razavet, C. J. Pickett, Chem. Eur. J. 2002, 8, 4037-4046). In support of this we find that computed and experimental IR frequencies of structurally characterised {2Fe3S} species and those of the bridging carbonyl intermediate are in excellent agreement. In a wider context, the study may provide some insight into the reactivity of dinuclear systems in which neighbouring group on-off coordination plays a role in substitution pathways.

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Section: }]mentioning

confidence: 99%

Dissecting the Intimate Mechanism of Cyanation of {2Fe3S} Complexes Related to the Active Site of All‐Iron Hydrogenases by DFT Analysis of Energetics, Transition States, Intermediates and Products in the Carbonyl Substitution Pathway

Zampella¹,

Bruschi²,

Fantucci³

et al. 2004

Chemistry A European J

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“…While the structure of the active site of [FeFe]-hydrogenase was first revealed at the late 1990s [46,47], a primitive structural model, dithiolate-bridged hexacarbonyl diiron complexe [(µ-SEt) 2 Fe 2 (CO) 6 ], was reported already in 1929 [48]. Modern models contain additional cyanide, phosphine or carbene ligands.…”

Section: Reactions Of [Fefe]-hydrogenase Models With Hydrogenmentioning

confidence: 99%

Hydrogen-activating models of hydrogenases

Chen

2015

Coordination Chemistry Reviews

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“…All thermal decompositions were made in an argon atmosphere. The compounds Fe 2 (CO) 6 S 2 , (1,2) 0021-9614/95/060605 + 07 $08.00/0Fe 2 (CO) 6 (SR) 2 (R is CH 3 or C 2 H 5 ), (6) and Fe 3 (CO) 9 S 2 , (6) were prepared according to the methods outlined in the literature. The compounds were purified by sublimation and characterised by microanalysis, and infrared and mass spectroscopy.…”

Section: Methodsmentioning

confidence: 99%

“…In this paper we report the results of a microcalorimetric study of the thermal decomposition of the simplest sulfur-containing derivatives of iron carbonyl. These compounds were first reported many years ago by Reihlen et al (1) and by Hieber and Scharfenberg. (2) The compounds have been fully characterised by spectroscopy (3) and crystallography.…”

Section: Introductionmentioning

confidence: 92%