Thermodynamic Scales for Sulfur Atom Transfer and Oxo-for-Sulfido Exchange Reactions

Donahue, James P.

doi:10.1021/cr050044w

Cited by 66 publications

(57 citation statements)

References 317 publications

(309 reference statements)

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“…We note that treatment of 1 with sulfur-atom-transfer (SAT) reagents such as propylene sulfide and Ph 3 SbS 32 led to no observable reaction. The five-membered chalcogen rings of 3 and 4 are favored over any other ring size, as treatment of 1 with >6 equiv.…”

Section: Resultsmentioning

confidence: 95%

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S₃˙⁻

et al. 2016

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Section: Resultsmentioning

confidence: 95%

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S₃˙⁻

et al. 2016

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“…Filling the "vacant" coordination site in Mo(L 3 ) 2 O by sulfur [98] instead of oxygen using propylene sulfide as sulfur atom donor [99] In the sequential sulfur atom transfer reaction the Mo O distances vary in accordance with the "spectator oxo effect" (Fig. 7) …”

Section: (O) 2 Complex Succeeds In (Slow) Quantitative Pme 3 Oxygenatmentioning

confidence: 99%

Bioinspired functional analogs of the active site of molybdenum enzymes: Intermediates and mechanisms

Heinze

2015

Coordination Chemistry Reviews

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“…Several studies have shown that triphenyl antimony sulfide (Ph 3 Sb=S) is useful for sulfur transfer reactions,9 including for the preparation of transition metal sulfide complexes 10,11. The utility of Ph 3 SbS likely stems from the thermodynamic instability of the Sb-S bond, which is weaker than the related bonds in R 3 E=S (E = P or As) congeners 12.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Ph₃Sb═S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity

2011

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In the exploration of sulfur-delivery reagents useful for synthesizing models of the tetracoppersulfide cluster of nitrous oxide reductase, reactions of Ph 3 Sb=S with Cu(I) complexes of N,N,N', and 1,4,7-trialkyltriazacyclononanes (R 3 tacn; R = Me, Et, iPr) were studied. Treatment of [(R 3 tacn)Cu(NCCH 3 )]SbF 6 (R = Me, Et, or iPr) with one equivalent of S=SbPh 3 in CH 2 Cl 2 yielded adducts [(R 3 tacn)Cu(S=SbPh 3 )]SbF 6 (1-3), which were fully characterized, including by X-ray crystallography. The adducts slowly decayed to [(R 3 tacn) 2 Cu 2 (µ-η 2 : η 2 -S 2 )] 2+ species (4-6) and SbPh 3 , or more quickly in the presence of additional [(R 3 tacn)Cu(NCCH 3 )]SbF 6 to 4-6 and [(R 3 tacn)Cu(SbPh 3 )]SbF 6 (7-9). The results of mechanistic studies of the latter process were consistent with rapid intermolecular exchange of S=SbPh 3 between 1-3 and added [(R 3 tacn)Cu(NCCH 3 )]SbF 6 , followed by conversion to product via a dicopper intermediate formed in a rapid pre-equilibrium step. Key evidence supporting this step came from the observation of saturation behavior in a plot of the initial rate of loss of 1 versus the initial concentration of [(Me 3 tacn)Cu(NCCH 3 )]SbF 6 . Also, treatment of [(TMCHD)Cu(CH 3 CN)]PF 6 with S=SbPh 3 led to the known tricopper cluster [(TMCHD) 3 Cu 3 (µ 3 -S) 2 ](PF 6 ) 3 in good yield (79%), a synthetic procedure superior to that previously reported (Brown, E. C.; York, J. T.; Antholine, W. E.; Ruiz, E.; Alvarez, S.; Tolman, W. B.

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Thermodynamic Scales for Sulfur Atom Transfer and Oxo-for-Sulfido Exchange Reactions

Cited by 66 publications

References 317 publications

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S₃˙⁻

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S₃˙⁻

Bioinspired functional analogs of the active site of molybdenum enzymes: Intermediates and mechanisms

Reactions of Ph₃Sb═S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity

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Thermodynamic Scales for Sulfur Atom Transfer and Oxo-for-Sulfido Exchange Reactions

Cited by 66 publications

References 317 publications

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙−

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙−

Bioinspired functional analogs of the active site of molybdenum enzymes: Intermediates and mechanisms

Reactions of Ph3Sb═S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity

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Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S₃˙⁻

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S₃˙⁻

Reactions of Ph₃Sb═S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity