Two silicon-bridged cyclopentadienyl Fe2S4 cluster units connected through an Fe(III)S6 unit. Crystal and molecular structure of [((CH3)2SiCp′2)2Fe5(μ3-S2)2(μ4-S2)2(μ4-S4)]FeCl4

Berg, Wouter van den; Boot, Coen; Linden, J.G.M. van der; Bosman, W. P.; Smits, J.M.; Beurskens, Paul T.; Heck, Juergen

doi:10.1016/0020-1693(93)03719-q

Cited by 13 publications

(6 citation statements)

References 17 publications

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“…The dihedral angle between the cyclopentadienyl rings is 91.98°, similar to those in related analogues: e.g. , 92.8°, cis -[(η 5 -C 5 H 5 ) 2 Fe 2 (CO) 4 ]; 97.2°, [(η 5 :η 5 -C 5 H 4 SiMe 2 C 5 H 4 )Fe 2 (CO) 4 ];3c 88.8°, [η 5 :η 5 -C 5 H 4 CH(NMe 2 )CH(NMe 2 )C 5 H 4 ]Fe 2 (CO) 4 …”

Section: Resultssupporting

confidence: 69%

“…These systems are suitable for studying interactions between two metal reaction sites, since the existence of a bridge inherently holds the two metals in close proximity. In particular, bridged bis(cyclopentadienyl)tetracarbonyldiiron derivatives, in which two (cyclopentadienyl)iron units are linked together by certain alkyl or silyl groups, have been receiving attention . Such bridging linkages result in special structural features and reactivity …”

Section: Introductionmentioning

confidence: 99%

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Novel Rearrangement Reactions. 1. Molecular Rearrangement via Metathesis between Intramolecular Si−Si and Fe−Fe Bonds

et al. 1997

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Thermal treatment of t-BuC5H4Me2SiSiMe2C5H4-t-Bu with Fe(CO)5 in xylene gave the diiron complex (Me2SiSiMe2)[(η5-t-BuC5H3)Fe(CO)]2(μ-CO)2 (3), existing as a mixture of cis and trans isomers (3c and 3t) which were separated by preparative TLC. When the two isomers were heated respectively in xylene, the cis substrate (3c) rearranged to the trans product [Me2Si(η5-t-BuC5H3)Fe(CO)2]2 (4t), while the trans substrate (3t) afforded the cis product [Me2Si(η5-t-BuC5H3)Fe(CO)2]2 (4c). This indicates that the rearrangement reaction is stereospecific. Complexes [(η5:η5-C5H4Me2SiSiMe2C5R3R‘)Fe(CO)]2(μ-CO)2 (R = H, R‘ = t-Bu, 5; R = R‘ = Me, 6), containing different cyclopentadienyl groups, were prepared similarly. Their respective rearrangement reactions only yielded the corresponding unsymmetrical products [(Me2Si)(η5-C5H4)Fe(CO)2][(Me2Si)(η5-C5R3R‘)Fe(CO)2] (R = H, R‘ = t-Bu, 7; R = R‘ = Me, 8); no symmetrical disproportionation products were detected. This indicates that the reaction proceeds via an intramolecular rather than intermolecular pathway. The conclusion is further confirmed by the fact that no crossover product was formed in subsequent rearrangement between two different substrates. Probing the reaction by ESR spectroscopy shows that the reaction proceeds via an intermediate containing iron-centered radicals. On the basis of these experimental facts, an alternative mechanism for the rearrangement reaction is proposed. Molecular structures of 3c, 3t, 4t, and 4c were determined by X-ray diffraction.

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Section: Resultssupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Novel Rearrangement Reactions. 1. Molecular Rearrangement via Metathesis between Intramolecular Si−Si and Fe−Fe Bonds

et al. 1997

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“…The geometry of 3 (Figure , Tables and ) differs only slighly from the geometry of 3 + 1 X-ray structure of [Me 2 Si(η 5 -C 5 H 4 ) 2 ] 2 Fe 5 S 12 ( 3 ).…”

Section: Resultsmentioning

confidence: 94%

“…Crystals of 3 ·CH 2 Cl 2 suitable for X-ray structure analysis were obtained by slow diffusion of hexane into a dichloromethane solution during a short period (1 week at room temperature). Earlier attempts to crystallize 3 from CH 2 Cl 2 /hexane mixtures at elevated temperatures over a longer period (8 weeks) had resulted in oxidative decomposition of 3 , yielding 3 + [FeCl 4 ] - …”

Section: Resultsmentioning

confidence: 99%

Iron−Sulfur Clusters with SiMe₂-Bridged Cyclopentadienyl Ligands: [Me₂Si(η⁵-C₅H₄)₂]₂Fe₅S₁₂, [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆, and [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆(CO)

et al. 1997

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The synthesis and characterization of iron-sulfur clusters stabilized by dimethylsilyl-bridged cyclopentadienyl groups are reported. The thermal reaction of Me(2)Si(eta(5)-C(5)H(4))(2)Fe(2)(CO)(4) (1) with S(8) yields the tetranuclear cubane-type cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6) (4) and the pentanuclear cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(5)S(12) (3) in high yields. The photochemical reaction of 1 with S(8) yields the tetranuclear cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6)(CO) (5), which contains one residual terminal carbonyl. The crystal structures of 3 and 4 have been determined. Crystal data: 3.CH(2)Cl(2), monoclinic, C2/c, a = 23.480(13) Å, b = 11.192 (4) Å, c = 17.84 (3) Å, beta = 118.58(9) degrees, V = 4118(7) Å(3), Z = 4, R = 0.078; 4, triclinic, P&onemacr;, a = 8.4787(7) Å, b = 12.9648(9) Å, c = 13.4990(9) Å, alpha = 79.857(8) degrees, beta = 75.293(8) degrees, gamma = 74.041(11) degrees, V = 1370.9(2) Å(3), Z = 2, R = 0.0447. The Fe(5)S(12) core of 3 has a bowtie structure in which a central iron atom is octahedrally coordinated by six sulfur atoms from one tetrasulfido and four disulfido groups. The structure of 4 resembles the structure of the known iron-sulfur cluster Cp(4)Fe(4)S(6). However, 4 shows a markedly enhanced thermal stability compared to Cp(4)Fe(4)S(6). In their cyclic voltammograms, 4 and 5 exhibit electrochemical behavior typical of cubane-type Cp-iron-sulfur clusters, whereas the cyclic voltammogram of 3 is quite different. The nu(CO) mode of 5 has been measured for four different oxidation states of the cluster by means of IR spectroelectrochemical methods. The Mössbauer spectra of 3 and 3(+) are in accordance with their pentanuclear structure.

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“…These systems are suitable for studying interactions between two metal reaction sites that are in close proximity. In particular, we have been interested in bridged biscyclopentadienyl tetracarbonyl diiron complexes in which two cyclopentadienyl ligands are linked together by certain alkyl or silyl groups . Compared to their nonbridged analogues, these complexes exhibit unique characteristics in both their structures and reactivity …”

Section: Introductionmentioning

confidence: 99%

Novel Rearrangement Reactions. 5. Thermal Rearrangement of Digermyl-Bridged Biscyclopentadienyl Diiron Complexes (Me₂GeGeMe₂)[(η⁵-C₅R₄)Fe(CO)]₂(μ-CO)₂ (R = H and Me)

et al. 1998

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Complexes (Me2GeGeMe2)[(η5-C5R4)Fe(CO)]2(μ-CO)2 (R = H, 1; Me, 3) 1 and 3, prepared by the reaction of C5R4HMe2GeGeMe2C5R4H with Fe(CO)5 in refluxing xylene, underwent a novel thermal reaction between their Ge−Ge and Fe−Fe bonds, forming corresponding rearrangement products with new cyclic structures, [Me2Ge(η5-C5R4)Fe(CO)2]2 (R = H, 2; Me 4). Compared with the case of silicon, the weaker Ge−Ge bond resulted in an easier rearrangement reaction. Reactions of 1 with iodine and sodium amalgam were examined. Molecular structures of 1, 2, 3, and 4 were determined by X-ray diffraction.

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Two silicon-bridged cyclopentadienyl Fe2S4 cluster units connected through an Fe(III)S6 unit. Crystal and molecular structure of [((CH3)2SiCp′2)2Fe5(μ3-S2)2(μ4-S2)2(μ4-S4)]FeCl4

Cited by 13 publications

References 17 publications

Novel Rearrangement Reactions. 1. Molecular Rearrangement via Metathesis between Intramolecular Si−Si and Fe−Fe Bonds

Novel Rearrangement Reactions. 1. Molecular Rearrangement via Metathesis between Intramolecular Si−Si and Fe−Fe Bonds

Iron−Sulfur Clusters with SiMe₂-Bridged Cyclopentadienyl Ligands: [Me₂Si(η⁵-C₅H₄)₂]₂Fe₅S₁₂, [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆, and [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆(CO)

Novel Rearrangement Reactions. 5. Thermal Rearrangement of Digermyl-Bridged Biscyclopentadienyl Diiron Complexes (Me₂GeGeMe₂)[(η⁵-C₅R₄)Fe(CO)]₂(μ-CO)₂ (R = H and Me)

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Two silicon-bridged cyclopentadienyl Fe2S4 cluster units connected through an Fe(III)S6 unit. Crystal and molecular structure of [((CH3)2SiCp′2)2Fe5(μ3-S2)2(μ4-S2)2(μ4-S4)]FeCl4

Cited by 13 publications

References 17 publications

Novel Rearrangement Reactions. 1. Molecular Rearrangement via Metathesis between Intramolecular Si−Si and Fe−Fe Bonds

Novel Rearrangement Reactions. 1. Molecular Rearrangement via Metathesis between Intramolecular Si−Si and Fe−Fe Bonds

Iron−Sulfur Clusters with SiMe2-Bridged Cyclopentadienyl Ligands: [Me2Si(η5-C5H4)2]2Fe5S12, [Me2Si(η5-C5H4)2]2Fe4S6, and [Me2Si(η5-C5H4)2]2Fe4S6(CO)

Novel Rearrangement Reactions. 5. Thermal Rearrangement of Digermyl-Bridged Biscyclopentadienyl Diiron Complexes (Me2GeGeMe2)[(η5-C5R4)Fe(CO)]2(μ-CO)2 (R = H and Me)

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Iron−Sulfur Clusters with SiMe₂-Bridged Cyclopentadienyl Ligands: [Me₂Si(η⁵-C₅H₄)₂]₂Fe₅S₁₂, [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆, and [Me₂Si(η⁵-C₅H₄)₂]₂Fe₄S₆(CO)

Novel Rearrangement Reactions. 5. Thermal Rearrangement of Digermyl-Bridged Biscyclopentadienyl Diiron Complexes (Me₂GeGeMe₂)[(η⁵-C₅R₄)Fe(CO)]₂(μ-CO)₂ (R = H and Me)