Hydrocarbon metal sulphide complexes IV. Some observations on the isomerisation of bis-μ-(arylthio)bis(carbonylcyclopentadienyliron)

Dekker, Margaret; Knox, G. R.; Robertson, Colin G.

doi:10.1016/s0022-328x(00)80244-2

Cited by 19 publications

(2 citation statements)

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“…However, stereochemical inversion at the S centers combined with Ni–carbene bond rotation will exchange all four isopropyl groups. Low sulfur inversion barriers have been reported for the μ-SR complexes {(dippe)Rh(μ-SPh)} 2 (7.7 kcal/mol) and {(dippe)Rh(μ-S( o -biphenyl))} 2 (14.7 kcal/mol), while a much higher barrier was reported for the terminal-SR complex {(Cp)(CO)Fe(μ-SPh)} 2 (30.7 kcal/mol) . Sulfur inversion barriers as low as 11.2 kcal/mol have been measured for Ru, Pd, and Pt thioether complexes …”

Section: Resultsmentioning

confidence: 97%

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}₂

et al. 2017

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Kinetic and DFT computational studies reveal that the reaction of {(IPr)Ni(μ-S)} (1, IPr = 1,3-bis(2,6-diisopropyl-phenyl)imidazolin-2-ylidene) with dihydrogen to produce {(IPr)Ni(μ-SH)} (2) proceeds by rate-limiting heterolytic addition of H across a Ni-S bond of intact dinuclear 1, followed by cis/trans isomerization at Ni and subsequent H migration from Ni to S, to produce the bis-hydrosulfide product 2. Complex 1 reacts in a similar manner with pinacolborane to produce {(IPr)Ni}(μ-SH)(μ-SBPin) (3), showing that heterolytic activation by this nickel μ-sulfide complex can be generalized to other H-E bonds.

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Section: Resultsmentioning

confidence: 97%

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}₂

et al. 2017

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“…The tert -butyl derivative has been observed only in the cis isomeric form, and it is assumed that steric considerations destabilize the trans isomer. The trans isomer of (η 5 -C 5 H 5 ) 2 Fe 2 (CO) 2 (μ-SPh) 2 re-equilibrates to the cis isomer by simple first-order kinetics . Activation energies were calculated to be 30.68 ± 0.60 kcal/mol in THF and 31.84 ± 0.54 kcal/mol in CS 2 .…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of cis/trans Isomerization of (η⁵-C₅H₅)₂Fe₂(CO)₂(μ-SR)₂, Where R = Methyl or tert-Butyl, Under Photochemical and Thermal Conditions

Bitterwolf

Scallorn

2000

Organometallics

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Photolysis of cis,syn-(η 5 -C 5 H 5 ) 2 Fe 2 (CO) 2 (µ-SMe) 2 and mixtures enriched in the trans,anti isomer in frozen Nujol matrixes at ca. 90 K has revealed a complex set of wavelengthdependent photoproducts. These photoproducts include three species with bridging carbonyl groups that appear to be a set of conformers differing in the relative orientation of the S-Me groups, a dicarbonyl species that may be a conformer of the trans,anti isomer, and two species that appear to have a single terminal carbonyl group. Evidence is also presented for the formation of an IR-silent intermediate, (η 5 -C 5 H 5 ) 2 Fe 2 (µ-SMe) 2 . Solution studies have demonstrated that the bridging carbonyl species are sufficiently stable to be observed at room temperature. These bridging isomers readily react with CO to mostly form the trans,anti isomer, providing one mechanism for cis to trans interchange. Photolysis of cis,syn-(η 5 -C 5 H 5 ) 2 -Fe 2 (CO) 2 (µ-SMe) 2 in petroleum ether under 13 CO at room temperature results in formation of both labeled and unlabeled trans,anti isomer, suggesting both a CO-loss and an internal non CO-loss pathway for isomer interconversion. Consistent with this, thermal reequilibration of trans,anti-enriched mixtures in petroleum ether under 13 CO results in formation of labeled trans,anti isomer, labeled (η 5 -C 5 H 5 )Fe(CO) 2 (SMe), and mostly unlabeled cis,syn isomer. Photolysis of cis,syn-(η 5 -C 5 H 5 ) 2 Fe 2 (CO) 2 (µ-S-t-Bu) 2 in frozen Nujol yields a bridging carbonyl photoproduct and the trans,anti isomer. Photolysis of the tert-butyl derivative in petroleum ether at 0 °C results in formation of the trans,anti isomer.

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Pyramidal Atomic Inversion

Lambert

1971

Topics in Stereochemistry

145

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Hydrocarbon metal sulphide complexes IV. Some observations on the isomerisation of bis-μ-(arylthio)bis(carbonylcyclopentadienyliron)

Cited by 19 publications

References 4 publications

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}₂

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}₂

Mechanisms of cis/trans Isomerization of (η⁵-C₅H₅)₂Fe₂(CO)₂(μ-SR)₂, Where R = Methyl or tert-Butyl, Under Photochemical and Thermal Conditions

Pyramidal Atomic Inversion

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Hydrocarbon metal sulphide complexes IV. Some observations on the isomerisation of bis-μ-(arylthio)bis(carbonylcyclopentadienyliron)

Cited by 19 publications

References 4 publications

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}2

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}2

Mechanisms of cis/trans Isomerization of (η5-C5H5)2Fe2(CO)2(μ-SR)2, Where R = Methyl or tert-Butyl, Under Photochemical and Thermal Conditions

Pyramidal Atomic Inversion

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Product

Resources

About

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}₂

Heterolytic H–H and H–B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}₂

Mechanisms of cis/trans Isomerization of (η⁵-C₅H₅)₂Fe₂(CO)₂(μ-SR)₂, Where R = Methyl or tert-Butyl, Under Photochemical and Thermal Conditions