Hydrosulfido complexes of transition metals

Kuwata, Shigeki; Hidai, Masanobu

doi:10.1016/s0010-8545(00)00375-1

Cited by 147 publications

(108 citation statements)

References 333 publications

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“…[7] Reduction of the disulfide bond of [(m-S 2 ){Fe(CO) 3 2À dianion, whose versatility has been amply demonstrated by the preparation of myriad diiron complexes containing features of the [FeFe]H 2 ase active site. [8] Protonation of the dianion with trifluoroacetic acid (2 equiv) by the method of Seyferth and co-workers yielded (m-SH) 2 [{Fe-(CO) 3 } 2 ]( 1)a nd shifted the n(CO) bands of the dianion by approximately + 50 cm À1 ,asexpected for the formation of the neutral SH derivative. [3] Theproduct 1 was an air-sensitive red solid with similar n(CO) values to those of its persulfide precursor,[(m-S 2 ){Fe(CO) 3 } 2 ](see Figure S1 in 2À .T he n(CO) values in the IR spectrum of 2 show ashift from those of the dianion by only about + 10 cm À1 (see Figure S1);t hat is,t here is an approximately 40 cm À1 difference as compared to 1.T his result implies more negative charge in the 2Fec ore of 2,a ss een in other S-bridged polymetallic diiron complexes,s uch as [(m 3 -S) 2 Ni(dppe){Fe-(CO) 3 ).…”

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confidence: 84%

“…Solid-state X-ray diffraction analysis found the two SAuPPh 3 and SH bridges in anti configurations.V TN MR studies,s upported by DFT computations,c onfirmed substantial barriers of approximately 25 kcal mol À1 to intramolecular interconversion between the three stereoisomers of [(m-SH) 2 {Fe(CO) 3 } 2 ]. In contrast, the largely dative SÀAu bond in mSAuPPh 3 facilitates inversion at Sa nd accounts for the facile equilibration of the SAuPPh 3 units,with an energy barrier half that of the SH analogue.T he reactivity of the gold-protected sulfur atoms of [(m-SAuPPh 3 ) 2 {Fe(CO) 3 Transition-metal sulfide clusters are presumed to have played an important role in energy metabolism even before the proliferation of life on planet Earth and before the paleoatmosphere became enriched in oxygen.…”

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confidence: 89%

“…,was found to serve as aproton surrogate and form as table Au 2 Fe 2 complex, [(m-SAuPPh 3 ) 2 {Fe(CO) 3 } 2 ], analogous to the highly reactive dihydrosulfide [(m-SH) 2 {Fe-(CO) 3 } 2 ]. Solid-state X-ray diffraction analysis found the two SAuPPh 3 and SH bridges in anti configurations.V TN MR studies,s upported by DFT computations,c onfirmed substantial barriers of approximately 25 kcal mol À1 to intramolecular interconversion between the three stereoisomers of [(m-SH) 2 {Fe(CO) 3 } 2 ].…”

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confidence: 99%

“…[2] Discrete hydrosulfido complexes can be synthesized through protonation of sulfido ligands,anexample of which is the protonation of the reduced, anionic sulfido-bridged species [(m-S) 2 {Fe(CO) 3 …”

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confidence: 99%

“…[4] The Ph 3 PAu + unit has also been used to model the protonation of metal-bound thiolates,w ith the generation of thiolatebridged M(m-SR)Au I moieties. [5] Herein we report the isolation of [(m-SAuPPh 3 ) 2 {Fe(CO) 3 2 Ni-(dppe){Fe(CO) 3 } 2 ]( dppe = 1,2-bis(diphenylphosphanyl)-ethane) were compared. [6] Interestingly,the stable polymetallic complexes can be used as synthons for [(m-SCH 2 N-(R)CH 2 S){Fe(CO) 3 } 2 ]t hrough the intermediacyo ft he highly unstable HS analogue;the azadithiolate is anecessary cofactor for the 2Fesubsite of [FeFe]H 2 ase.…”

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A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions

et al. 2015

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[1] These complexes could therefore be early abiotic analogues of the diiron hydrogenase ([FeFe]-H 2 ase) active site (Figure 1), to be later replaced by biosynthetic paths required for protection of the organism from the toxic diatomic ligands in the [FeFe]H 2 ase active site.I nf act, [(m-S 2 ){Fe(CO) 3 } 2 ]e njoys current fame as the synthetic precursor to ah ost of small molecules that are biomimetic analogues of the active site of [FeFe]H 2 ase,t hus connecting the inorganic to the biological world, through organometallic chemistry (Figure 1).Studies of SH À as al igand are of importance to the bioinorganic chemistry of iron;h owever,e xamples and studies of isolated Fe À SH units are sparse.[2] Discrete hydrosulfido complexes can be synthesized through protonation of sulfido ligands,anexample of which is the protonation of the reduced, anionic sulfido-bridged species [(m-S) 2 {Fe(CO) 3 } 2 ] 2À to form [(m-SH) 2 {Fe(CO) 3 } 2 ].[3] Although the spectroscopic signatures (n(CO) and NMR spectra) of [(m-SH) 2 {Fe(CO) 3 } 2 ] have been known for decades,i ts X-ray crystal structure has not been reported until now.Because of the well-known isolobal analogy between Ph 3 PAu + and H + ,the former may serve as asurrogate for the latter,t hus leading to experimental strategies particularly useful in the structural determination of many organometallic compounds containing transition-metal hydrides.[4] The Ph 3 PAu + unit has also been used to model the protonation of metal-bound thiolates,w ith the generation of thiolatebridged M(m-SR)Au I moieties.[5] Herein we report the isolation of [(m-SAuPPh 3 ) 2 {Fe(CO) 3 } 2 ]and [(m-SH) 2 {Fe(CO) 3 } 2 ], and their characterization by X-ray diffraction. Thes pectroscopic properties and chemical reactivity of these two complexes as well as the nickelated complex [(m 3 -S) 2 Ni-(dppe){Fe(CO) 3 } 2 ]( dppe = 1,2-bis(diphenylphosphanyl)-ethane) were compared.[6] Interestingly,the stable polymetallic complexes can be used as synthons for [(m-SCH 2 N-(R)CH 2 S){Fe(CO) 3 } 2 ]t hrough the intermediacyo ft he highly unstable HS analogue;the azadithiolate is anecessary cofactor for the 2Fesubsite of [FeFe]H 2 ase. [7] Reduction of the disulfide bond of [(m-S 2 ){Fe(CO) 3 } 2 ]b y LiEt 3 BH (2 equiv) in THF at À78 8 8Cp roduces the [(m-S) 2 {Fe(CO) 3 } 2 ]2À dianion, whose versatility has been amply demonstrated by the preparation of myriad diiron complexes containing features of the [FeFe]H 2 ase active site.[8] Protonation of the dianion with trifluoroacetic acid (2 equiv) by the method of Seyferth and co-workers yielded (m-SH) 2 [{Fe-(CO) 3 } 2 ]( 1)a nd shifted the n(CO) bands of the dianion by approximately + 50 cm À1 ,asexpected for the formation of the neutral SH derivative.[3] Theproduct 1 was an air-sensitive red solid with similar n(CO) values to those of its persulfide precursor,[(m-S 2 ){Fe(CO) 3 } 2 ](see Figure S1 in 2À .T he n(CO) values in the IR spectrum of 2 show ashift from those of the dianion by only about + 10 cm À1 (see Figure S1);t hat is,t here is an approxim...

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confidence: 84%

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confidence: 89%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions

et al. 2015

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Molybdenum: Organometallic ChemistryBased in part on the article Molybdenum: Organometallic Chemistry by M. David Curtis which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Flower¹

2005

Encyclopedia of Inorganic Chemistry

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This article considers only compounds that contain a direct molybdenum‐to‐carbon bond. Because of the size of the topic and the large number of publications each year, the article gives a general overview of major current areas of interest in molybdenum‐centered organometallic chemistry. The material is presented in three major sections: σ‐ligand‐containing complexes, which covers alkyl‐, carbonyl‐, halocarbonyl‐, alkylidenes‐, and alkylidyne complexes, heavier group 14 analogs of alkylidene and alkylidyne complexes; π‐ligand‐containing complexes, which covers alkene‐, polyene‐, alkyne‐, phosphaalkyne‐containing complexes, along with π‐bound cyclic organic systems such as cyclobutadiene, cyclopentadienyl, and arenes; polymetallic complexes and multiply bonded systems are also discussed. Each section considers the major methods of preparation of compounds containing that ligand class and surveys the major types of reaction they undergo, both metal‐ and ligand‐centered, along with the factors that influence the products that form. Where data is available, solid‐state structural data are presented to aid in the discussion of the material presented.

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S ‐Donor Ligands

Collinson

Schröder

2005

Encyclopedia of Inorganic Chemistry

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The chemistry of S‐donor ligands with metal centres is reviewed with emphasis placed on the structures and redox activity of the resultant complexes. Sulfides and thiolates bind to a wide range of metal ions. The oxidation of thiolates to sulfones and sulfoxides and the structures and chemistry of metal‐thiolene complexes are detailed. Thioethers are generally poor ligands for transition metal ions but macrocylic ligands afford stable complexes. Many metalloproteins contain metal–sulfur bonds and the structures of many of these have now been elucidated. This has sparked a renaissance in the synthesis of low‐molecular weight metal complex mimics.

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Hydrosulfido complexes of transition metals

Cited by 147 publications

References 333 publications

A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions

A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions

Molybdenum: Organometallic ChemistryBased in part on the article Molybdenum: Organometallic Chemistry by M. David Curtis which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

S ‐Donor Ligands

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