The molybdenum-molybdenum triple bond. 14. Preparation and characterization of mixed alkoxy-thiolate compounds of formula Mo2(OR)2(SAr)4 (M.tplbond.M)

Chisholm, Malcolm H.; Corning, James F.; Huffman, John C.

doi:10.1021/ic00174a023

Cited by 25 publications

(9 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…where coordination modes of Fe 2 (µ-S 2 )(CO) 6 molecules to the Mo atom are almost the same as that in 4. Such short Mo-S bonds in 4 indicate the existence of sulfur to molybdenum π-bonding, 19 which may compensate for the decrease of electrons in 4.…”

Section: Resultsmentioning

confidence: 99%

Reaction of CpW(CO)₂(μ-PPh₂)Mo(CO)₅ and Fe₂(μ-S₂)(CO)₆: Unusual Fragmentation and Coordination of Fe₂(μ-S₂)(CO)₆

2004

View full text Add to dashboard Cite

Reaction of Fe2(μ-S2)(CO)6 with at dichloromethane reflux afforded heterotrimetallic clusters CpW(μ-PPh2)Mo(CO)3(μ-CO)(μ3-S)2Fe2(CO)5 (1), Cp(CO)W(μ-PPh2)Mo(CO)3(μ3-S)2Fe(CO)3 (2), CpW(μ-PPh2)Mo(CO)3(μ3-S)2Fe2(μ-CO)(CO)4 (3), and CpW(CO)(μ3-S)2Fe(μ-PPh2)Fe(CO)4Mo(μ3-S)2Fe2(CO)6 (4). Thermolysis of 1 in dichloromethane produced 3, which was also obtained by the reaction of 2 with Fe2(CO)9 at dichloromethane reflux. Reflux of a benzene solution of 3 with norbornadiene (nbd) produced CpW(μ-PPh2)Mo(CO)(nbd)(μ3-S)2Fe2(μ-CO)(CO)4 (5), but the typical reaction without nbd afforded a benzene substitution product, CpW(μ-PPh2)Mo(η6-C6H6)(μ3-S)2Fe2(μ-CO)(CO)4 (6). Molecular structures of 1−6 were determined by single-crystal X-ray diffraction analyses. Cluster 1 has bitetrahedral geometry, where the Fe2MoW core is intercepted by an Fe−W bond to FeMoW and Fe2W units, and each unit is capped by a μ3-S atom. Cluster 2 is a rare example of square pyramidal geometry with the FeS2W plane capped by a Mo atom, whereas cluster 3 consists of an Fe2MoW tetrahedron core with each FeMoW face capped by a μ3-S atom. Clusters 4−6 possess an Fe2MoW core geometry similar to that of 3, where carbonyl ligands on the Mo site were replaced by Fe2(μ-S2)(CO)6, nbd, and benzene, respectively.

show abstract

Section: Resultsmentioning

confidence: 99%

Reaction of CpW(CO)₂(μ-PPh₂)Mo(CO)₅ and Fe₂(μ-S₂)(CO)₆: Unusual Fragmentation and Coordination of Fe₂(μ-S₂)(CO)₆

2004

View full text Add to dashboard Cite

show abstract

“…This indicates that the sulfido ligand has a strong trans effect compared to that of the phosphido ligand. Such a short Mo tr −S (2.3023(15) Å) distance trans to the sulfido ligand indicates the existence of sulfur to molybdenum π bonding …”

Section: Resultsmentioning

confidence: 99%

Thiolate Ligand Transfer from Metallothiolates to Phosphido-Bridged Heterobimetallic Compounds: C−S Bond Cleavage in Benzenethiol and Formation of a Mixed-Metal Trinuclear Compound

2003

View full text Add to dashboard Cite

Thiolate ligand transfer occurred during the reaction between CpMo(CO) 3 SPh and CpW-(CO) 2 (µ-PPh 2 )Mo(CO) 5 ( 1) in dichloromethane at reflux, resulting in the new mixed-metal and mixed-ligand bridged compound CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO) 3 (2). However, when CpW(CO) 3 SPh reacted with 1 under similar conditions, 2 and the mixed-metal trinuclear compound CpW(CO)(µ-S) 2 (µ-PPh 2 )Mo(CO) 2 (µ-PPh 2 )W(CO) 2 Cp (4) were formed. The presence of the (µ-S) 2 bridges in 4 indicates C-S bond cleavage in the SPh ligand. Reflux of a dichloromethane solution of 1 and PhSH also produced 2 along with CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO)(SPh) 2 (3) and CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO) 2 (PPh 2 H) (5). Moreover, the same reactants in benzene at reflux gave 2, 3, 5, and the additional product CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO) 2 (PPh 3 ) (6). The reaction of 1 with Ph 2 S 2 in dichloromethane at reflux produced compounds 2 and 3. Similarly conducted reactions in benzene at reflux afforded 2, 3, and 6. Compounds 2-6 were characterized by single-crystal X-ray diffraction analyses. Formation of the PPh 3 ligand, which coordinated to 6, suggests C-S bond cleavage in PhSH and Ph 2 S 2. Compounds 3, 5, and 6 were also synthesized in high yield by refluxing 2 with PhSH or Ph 2 S 2 , PPh 2 H, and PPh 3 , respectively, in benzene.

show abstract

“…(Bu 4 N) 2 [(Smes)Fe 4 S 4 (LS 3 )]. To a solution of 17.5 mg (9.51 μmol) of (Bu 4 N) 2 [Fe 4 S 4 (LS 3 )(SEt)] in 2 mL of acetonitrile was added a solution of 2.72 μL (17.9 μmol) of mesitylenethiol in 0.5 mL of acetonitrile. The resulting solution was stirred for 30 min, and solvent was removed in vacuo to leave a black solid.…”

Section: Experimental Section29mentioning

confidence: 99%

Metal Ion Incorporation Reactions of the Cluster [Fe₃S₄(LS₃)]³^-, Containing the Cuboidal [Fe₃S₄]⁰ Core

et al. 1997

View full text Add to dashboard Cite

The frequent occurrence of the cuboidal cluster [Fe3S4(S·Cys)3] in a variety of proteins has prompted extensive investigation of its chemical and biological properties. The biological function remains in question, but the cluster is known to sustain two reactions: (i) electron transfer, and (ii) heterometal ion incorporation. The recent preparation of [Fe3S4(LS3)]3- (3) [Zhou, J.; Hu, Z.; Münck, E.; Holm, R. H. J. Am. Chem. Soc. 1996, 118, 1966] has permitted detailed structural, electronic, and reactivity characterization of the cuboidal [Fe3S4]0 oxidation state (LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3−). Redox properties (i) have been reported previously: here reaction type (ii), resulting in the formation of cubane-type MFe3S4 clusters, has been investigated. Reaction of 3 with [M(PPh3)4]1+ affords [(Ph3P)MFe3S4(LS3)]2- (M = Cu (6), Ag (8)) while [(NC)M(PPh3)3] leads to [(NC)MFe3S4(LS3)]3- (M = Cu (7), Ag (9)). Treatment of 3 with Tl(O3SCF3) yields [TlFe3S4(LS3)]2- (10). The fragment formalism {M1+ + [Fe3S4]0} applies to 6−10, which retain the S = 2 ground state of 3. Reaction of 3 with [M(PPh3)3Cl] yields [(Ph3P)MFe3S4(LS3)]2- (M = Co (12), Ni (14)) in inner-sphere redox reactions. Clusters 12 (S = 1) and 14 (S = 3/2) are formulated as {M2+ + [Fe3S4]1-}; antiferromagnetic coupling of fragment spins gives rise to the indicated spin ground states. The reactions (ii) are metal-ion incorporation processes, a new reaction type in Fe−S chemistry. Previously, all cubane-type MFe3S4 clusters had been synthesized by spontaneous self-assembly or reductive rearrangement reactions. Cluster 7 exhibits reversible oxidation and reduction reactions; it is the only cluster that forms a stable oxidized product containing the [Fe3S4]1+ fragment. All other clusters show a reversible reduction and an irreversible or quasireversible oxidation. Potentials of the synthetic clusters are considered intrinsic to the various core units, being less influenced by environmental factors than are those in proteins. At parity of cluster charge and terminal ligation, the potential order is M = Fe < Co < Ni and Co < Ni < Cu < Ag < Tl for the [MFe3S4]2+,1+ and [MFe3S4]1+,0 core redox reactions. These orders are compared with those determined in proteins.

show abstract

The molybdenum-molybdenum triple bond. 14. Preparation and characterization of mixed alkoxy-thiolate compounds of formula Mo2(OR)2(SAr)4 (M.tplbond.M)

Cited by 25 publications

References 1 publication

Reaction of CpW(CO)₂(μ-PPh₂)Mo(CO)₅ and Fe₂(μ-S₂)(CO)₆: Unusual Fragmentation and Coordination of Fe₂(μ-S₂)(CO)₆

Reaction of CpW(CO)₂(μ-PPh₂)Mo(CO)₅ and Fe₂(μ-S₂)(CO)₆: Unusual Fragmentation and Coordination of Fe₂(μ-S₂)(CO)₆

Thiolate Ligand Transfer from Metallothiolates to Phosphido-Bridged Heterobimetallic Compounds: C−S Bond Cleavage in Benzenethiol and Formation of a Mixed-Metal Trinuclear Compound

Metal Ion Incorporation Reactions of the Cluster [Fe₃S₄(LS₃)]³^-, Containing the Cuboidal [Fe₃S₄]⁰ Core

Contact Info

Product

Resources

About

The molybdenum-molybdenum triple bond. 14. Preparation and characterization of mixed alkoxy-thiolate compounds of formula Mo2(OR)2(SAr)4 (M.tplbond.M)

Cited by 25 publications

References 1 publication

Reaction of CpW(CO)2(μ-PPh2)Mo(CO)5 and Fe2(μ-S2)(CO)6: Unusual Fragmentation and Coordination of Fe2(μ-S2)(CO)6

Reaction of CpW(CO)2(μ-PPh2)Mo(CO)5 and Fe2(μ-S2)(CO)6: Unusual Fragmentation and Coordination of Fe2(μ-S2)(CO)6

Thiolate Ligand Transfer from Metallothiolates to Phosphido-Bridged Heterobimetallic Compounds: C−S Bond Cleavage in Benzenethiol and Formation of a Mixed-Metal Trinuclear Compound

Metal Ion Incorporation Reactions of the Cluster [Fe3S4(LS3)]3-, Containing the Cuboidal [Fe3S4]0 Core

Contact Info

Product

Resources

About

Reaction of CpW(CO)₂(μ-PPh₂)Mo(CO)₅ and Fe₂(μ-S₂)(CO)₆: Unusual Fragmentation and Coordination of Fe₂(μ-S₂)(CO)₆

Reaction of CpW(CO)₂(μ-PPh₂)Mo(CO)₅ and Fe₂(μ-S₂)(CO)₆: Unusual Fragmentation and Coordination of Fe₂(μ-S₂)(CO)₆

Metal Ion Incorporation Reactions of the Cluster [Fe₃S₄(LS₃)]³^-, Containing the Cuboidal [Fe₃S₄]⁰ Core