The Structure of Derivatives of [SCH3Fe(CO)3]2

Crow, John P.; Cullen, William R.

doi:10.1139/v71-493

Cited by 23 publications

(8 citation statements)

References 8 publications

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“…77 The isomerization of ee -Fe 2 ( μ -SMe) 2 (CO) 6 to ae -Fe 2 ( μ -SMe) 2 (CO) 6 is intramolecular. 80,81 The barrier for isomerization is higher for small alkyl groups, such as Me, Et, and Bn. For t -Bu, the barrier is sufficiently low (17 kcal/mol) that the dynamic interconversion of the ae and ee isomers can be observed by NMR at 100 °C.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

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Virtually all organosulfur compounds react with Fe(0) carbonyls to give the title complexes. These reactions are reviewed in light of major advances over the past few decades, spurred by interest in Fe2(μ-SR)2(CO)x centers at the active sites of the [FeFe]-hydrogenase enzymes. The most useful synthetic route to Fe2(μ-SR)2(CO)6 involves the reaction of thiols with Fe2(CO)9 and Fe3(CO)12. Such reactions can proceed via mono-, di-, and triiron intermediates. The reactivity of Fe(0) carbonyls toward thiols is highly chemoselective, and the resulting dithiolato complexes are fairly rugged. Thus, many complexes tolerate further synthetic elaboration directed at the organic substituents. A second major route involves alkylation of Fe2(μ-S2)(CO)6, Fe2(μ-SH)2(CO)6, and Li2Fe2(μ-S)2(CO)6. This approach is especially useful for azadithiolates Fe2[(μ-SCH2)2NR](CO)6. Elaborate complexes arise via addition of the FeSH group to electrophilic alkenes, alkynes, and carbonyls. Although the first example of Fe2(μ-SR)2(CO)6 was prepared from ferrous reagents, ferrous compounds are infrequently used, although the Fe(II)(SR)2 + Fe(0) condensation reaction is promising. Almost invariably low-yielding, the reaction of Fe3(CO)12, S8, and a variety of unsaturated substrates results in C–H activation, affording otherwise inaccessible derivatives. Thiones and related C═S-containing reagents are highly reactive toward Fe(0), often giving complexes derived from substituted methanedithiolates and C–H activation.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

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“…A number of iron carbonyl derivatives of fluorocarbon-bridged ditertiary arsines and phosphines have been described in recent years (1)(2)(3)(4). Of special interest have been the complexes formed by f4fars and f4fos la and lb.…”

Section: Introductionmentioning

confidence: 99%

The Preparation of Iron Carbonyl Complexes of Fluorocarbon-Bridged Ligands

Chia¹,

Cullen²,

Harbourne³

1972

Can. J. Chem.

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The reactions of the ligands [Formula: see text] L′ = (CH3)2As, (C6H5)2P; n = 4, 6, 8; but not all combinations) with iron carbonyls are described in detail. The nature of the products is discussed as a function of the reaction conditions and the ligands. The mixed ligands yield eight different types of complexes which have been characterized. Two of these types (L—L′)2Fe2(CO)4. and (L—L′)2Fe(CO)3 were previously unknown.

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“…This investigation complen~ents our studies on ligand substitution reactions of other derivatives of cobalt (4,5) and iron carbonyls (6).…”

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confidence: 63%

“…arphos or f4AsP, these consideratioris also lead In those cases where only two lines could be to the conciusion that the phosphorus atom is resolved in the Miissbauer sDectra there was bonded to Fe" and the arsenic atom to FeB. usually considerable broadening of one or both Two of these derivatives, namely Cf4fosIb-lines, so that the 6 and jdEQ1 values for the t~l o (f4fos)Fe2(C0)4 and (~~A S P )~(~~A S P ) F~~( C Q )~, iron atoms must be slightly different. The were studied by magnetic-perturbation Mossparameter values given in Table 4 former complex at 4.2 K in a longitudinal magnetic field of 50 kG is shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Disubstituted derivatives of (L—L)Fe₂(CO)₆ (L—L = fluorocarbon bridged ligand)

Chia¹,

Cullen²,

Sams³

et al. 1976

Can. J. Chem.

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The complexes (L—L)Fe2(CO)6 react with a range of bidentate ligands to give the complexes (L—L)′(L—L)Fe2(CO)4 ((L—L) = fluorocarbon-bridged ligand such as f4fars, f4AsP etc. (L—L)′ = fluorocarbon- and hydrocarbon-bridged ligands such as f4AsP diars etc.). Spectroscopic studies, in particular magnetically perturbed Mössbauer measurements, indicate that (L—L)′ in most complexes is chelated to one iron atom, FeA. This leaves one CO group on FeAcis to the FeA—FeB bond and three on FeB. A smaller class of derivatives appear to have (L—L)′ bridging the two iron atoms cis to the FeA—FeB bond. The sign of Vzz is positive at both iron sites in the bridged derivatives. It is negative at FeA and positive at FeB in the other complexes.

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The Structure of Derivatives of [SCH₃Fe(CO)₃]₂

Cited by 23 publications

References 8 publications

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

The Preparation of Iron Carbonyl Complexes of Fluorocarbon-Bridged Ligands

Disubstituted derivatives of (L—L)Fe₂(CO)₆ (L—L = fluorocarbon bridged ligand)

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The Structure of Derivatives of [SCH3Fe(CO)3]2

Cited by 23 publications

References 8 publications

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

The Preparation of Iron Carbonyl Complexes of Fluorocarbon-Bridged Ligands

Disubstituted derivatives of (L—L)Fe2(CO)6 (L—L = fluorocarbon bridged ligand)

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The Structure of Derivatives of [SCH₃Fe(CO)₃]₂

Disubstituted derivatives of (L—L)Fe₂(CO)₆ (L—L = fluorocarbon bridged ligand)