Synthesis and structure of (Bu4N)[MoO(O2CC(S)Ph2)2]. The first mononuclear molybdenum(V) complex containing both coordinated thiolate and carboxylate groups

Sanz, Vicente Claramonte; Picher, T.; Palanca, Pedro; Gómez‐Romero, Pedro; Llopis, Elisa; Ramírez, José A.; Beltrán, Daniel; Cervilla, Antonio

doi:10.1021/ic00016a001

Cited by 28 publications

(10 citation statements)

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“…The addition of 2.5 equiv of H 2 L (as required by the reaction stoichiometry) results in a higher yield of 1, typically with isolation of 65±70% of 1. The synthesis of Mo(V) complexes from Mo(VI) precursors via thiol-induced reduction has been seen in other systems [40,45,52,53,54]. The Et 4 N + , PPh 4 + , and Bu 4 N + salts of [Mo(O)L 2 ] ± have also been prepared.…”

Section: Resultsmentioning

confidence: 94%

A mononuclear molybdenum(V) mono-oxo biphenyl-2,2′-dithiolate complex in which the metal resides within a cleft formed by the ligands and that exhibits N-H...S hydrogen bonding in the solid state

Conry

Tipton

2001

J. Biol. Inorg. Chem.

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The reaction of Mo(O)2(acac)2, H2L (2,2'-dimercaptobiphenyl), and NEt3 produced the mononuclear Mo(V) complex Et3NH[Mo(O)(L)2] (1). Molybdenum mono-oxo tetrathiolate complexes such as 1 are studied as potential structural or functional models for pyranopterin-containing molybdoenzymes. Complex 1 has been crystallographically characterized. The solid-state structure reveals that the molybdenum ion sits within a cleft formed by the biphenyl backbone of the ligands, providing some steric protection. In addition, there is a hydrogen bond between the amine hydrogen of [Et3NH]+ and one of the thiolate sulfur atoms. A difference in solution reactivity between 1 and a derivative without a hydrogen-bonding counterion suggests that hydrogen bonding occurs in solution also. There are two short S-S contacts and small S-Mo-S angles in the structure of 1 that may reflect a slight bonding interaction. Such short S-S distances and small angles have been found in a couple of other Mo-thiolate complexes and in many of the molybdoenzyme crystal structures. Further characterization of 1 by EPR, IR, and UV-vis spectroscopies, as well as by cyclic voltammetry, is discussed and compared to known Mo(V)-oxo-tetrathiolate complexes as well as to relevant molybdoenzyme data. Reactions to generate Mo(VI) complexes from 1 resulted in net oxidation at the ligand to form its disulfide derivative, which dissociated from the metal center. This result suggests that modifications to the ligand to prevent this process are needed.

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Section: Resultsmentioning

confidence: 94%

A mononuclear molybdenum(V) mono-oxo biphenyl-2,2′-dithiolate complex in which the metal resides within a cleft formed by the ligands and that exhibits N-H...S hydrogen bonding in the solid state

Conry

Tipton

2001

J. Biol. Inorg. Chem.

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“…Spectrophotonzetric Measurements.-Martin and Spence ' reported reaction (4). from which molybdenum-containing products were isolated.…”

Section: Resultsmentioning

confidence: 99%

Structure and electrochemical properties of the new triply bridged molybdenum(V) complex [NBuⁿ₄]₂[Mo₂O₂(µ-O)(SCH₂CO₂)₂(µ-SCH₂CO₂)]

Cervilla¹,

Llopis²,

Ramírez³

et al. 1994

J. Chem. Soc., Dalton Trans.

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“…Figure13. Effect of [Ag33+]" cluster aggregation on the frontier orbital energies: +, LUMO (no charge iterations (Cl)); D, HOMO (no Cl); , LUMO (Cl); O, HOMO (Cl).…”

mentioning

confidence: 99%

Class B sodalites: nonstoichiometric silver, sodium halosodalites

Stein¹,

Ozin²,

Stucky³

1992

J. Am. Chem. Soc.

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Synthesis and structure of (Bu4N)[MoO(O2CC(S)Ph2)2]. The first mononuclear molybdenum(V) complex containing both coordinated thiolate and carboxylate groups

Cited by 28 publications

References 1 publication

A mononuclear molybdenum(V) mono-oxo biphenyl-2,2′-dithiolate complex in which the metal resides within a cleft formed by the ligands and that exhibits N-H...S hydrogen bonding in the solid state

A mononuclear molybdenum(V) mono-oxo biphenyl-2,2′-dithiolate complex in which the metal resides within a cleft formed by the ligands and that exhibits N-H...S hydrogen bonding in the solid state

Structure and electrochemical properties of the new triply bridged molybdenum(V) complex [NBuⁿ₄]₂[Mo₂O₂(µ-O)(SCH₂CO₂)₂(µ-SCH₂CO₂)]

Class B sodalites: nonstoichiometric silver, sodium halosodalites

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Synthesis and structure of (Bu4N)[MoO(O2CC(S)Ph2)2]. The first mononuclear molybdenum(V) complex containing both coordinated thiolate and carboxylate groups

Cited by 28 publications

References 1 publication

A mononuclear molybdenum(V) mono-oxo biphenyl-2,2′-dithiolate complex in which the metal resides within a cleft formed by the ligands and that exhibits N-H...S hydrogen bonding in the solid state

A mononuclear molybdenum(V) mono-oxo biphenyl-2,2′-dithiolate complex in which the metal resides within a cleft formed by the ligands and that exhibits N-H...S hydrogen bonding in the solid state

Structure and electrochemical properties of the new triply bridged molybdenum(V) complex [NBun4]2[Mo2O2(µ-O)(SCH2CO2)2(µ-SCH2CO2)]

Class B sodalites: nonstoichiometric silver, sodium halosodalites

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Structure and electrochemical properties of the new triply bridged molybdenum(V) complex [NBuⁿ₄]₂[Mo₂O₂(µ-O)(SCH₂CO₂)₂(µ-SCH₂CO₂)]