Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Hossain, Md. Munkir; Lin, Hsiu‐Mei; Shyu, Shin‐Guang

doi:10.1002/1099-0682(200109)2001:10<2655::aid-ejic2655>3.0.co;2-n

Cited by 15 publications

(14 citation statements)

References 47 publications

(23 reference statements)

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“…The transmetalation reaction occurs with transfer of the Cp ligand in the case of the reaction CpFe(CO) 2 SPh + M(CO) 5 (THF) (M = Mo, W). 313 The heterometallic intermediate was crystallized for the W–Fe case. The presumed transformations are summarized in eqs 19 and 20.…”

Section: Synthesis Of Diiron(i) Dithiolato Carbonyls From Iron(0) mentioning

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: Synthesis Of Diiron(i) Dithiolato Carbonyls From Iron(0) mentioning

confidence: 99%

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

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“…(Para‐substituted benzenethiolato)dicarbonyl( η 5 ‐cyclopentadienyl) iron ( p ‐G‐C 6 H 4 S( η 5 ‐C 5 H 5 )(CO) 2 Fe, abbreviated as p ‐G‐C 6 H 4 SFp, where G = NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 ) complexes constitute an important class of compounds and have received considerable attention particularly because of their involvement in many synthetic processes. For example, the simple metallothioether FpSPh is obviously a good ligand for mimicking the real, complicated metallothioether ligand Cys‐SFe 4 S 4 (SCys) 3 in the H cluster of [Fe]H 2 ases .…”

Section: Introductionmentioning

confidence: 99%

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

Zeng

Dong

et al. 2013

J of Physical Organic Chem

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Metal-ligand bond enthalpy data can afford invaluable insights into important reaction patterns in organometallic chemistry and catalysis. In this paper, the Fe-O and Fe-S homolytic bond dissociation energies [ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s] of two series of para-substituted phenoxydicarbonyl(h 5 -cyclopentadienyl) iron [p-G-C 6 H 4 OFp (1)] and (para-substituted benzenethiolato)dicarbonyl(h 5 -cyclopentadienyl) iron [p-G-C 6 H 4 SFp (2)] were studied using Hartree-Fock and density functional theory (DFT) methods with large basis sets. In this study, Fp is (h 5 -C 5 H 5 )Fe(CO) 2 , and G are NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 . The results show that DFT methods can provide the best price/performance ratio and accurate predictions of ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s. The remote substituent effects on ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s [ΔΔH homo (Fe-O)'s and ΔΔH homo (Fe-S)'s] can also be satisfactorily predicted. The good correlations [r = 0.98 (g, 1), 0.98 (g, 2)] of ΔΔH homo (Fe-O)'s and ΔΔH homo (Fe-S)'s in series 1 and 2 with the substituent s p + constants imply that the para-substituent effects on ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔH homo (Fe-O)'s (1) and ΔΔH homo (Fe-S)'s (2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes.

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“…Organotungsten complexes supported by sulfur-donor ligands have attracted continuous interest in recent years [1][2][3][4]. The thiolato complexes CpW(CO) 2 (L)SR (L = CO, PPh 3 ) are accessible by several routes [5][6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

“…Oxidation of some of these tungsten thiolates by 3-chloroperoxybenzoic acid gave the sulfinato complexes CpW(CO) 2 (L)SO 2 R [11]. Photolysis using UV-light or heating solutions of the tricarbonyltungsten thiolates produced the thiolato-bridged dimers (l-SR) 2 [CpW(CO) 2 ] 2 [12].…”

Section: Introductionmentioning

confidence: 99%

Cyclopentadienyl tungsten complexes with thiocarboxylate and thiosulfonate ligands: Structures of CpW(CO)3SCOPh and CpW(CO)3SSO2-4-C6H4Cl

El‐khateeb

Görls

Weigand

2006

Journal of Organometallic Chemistry

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Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Cited by 15 publications

References 47 publications

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods

Cyclopentadienyl tungsten complexes with thiocarboxylate and thiosulfonate ligands: Structures of CpW(CO)3SCOPh and CpW(CO)3SSO2-4-C6H4Cl

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Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Cited by 15 publications

References 47 publications

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

Cyclopentadienyl tungsten complexes with thiocarboxylate and thiosulfonate ligands: Structures of CpW(CO)3SCOPh and CpW(CO)3SSO2-4-C6H4Cl

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Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C₆H₄OFe(CO)₂(η⁵‐C₅H₅) and p‐G‐C₆H₄SFe(CO)₂(η⁵‐C₅H₅) studied using Hartree–Fock and density functional theory methods