Electronic properties of thiolate compounds of oxomolybdenum(V) and their tungsten and selenium analogs. Effects of oxygen-17, molybdenum-98, and molybdenum-95 isotope substitution upon ESR spectra

Hanson, Graeme R.; Brunette, Andrew A.; McDonell, Angus C.; Murray, Keith S.; Wedd, Anthony G.

doi:10.1021/ja00398a013

Cited by 125 publications

(90 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thiolate-to-metal transitions are observed in other Mo(V)-oxo-tetrathiolate complexes from 436 to 729 nm [43,44,45,47,56,57,58,59,60,61,62]. The Mo(V) tetrathiolate complexes that give the highest energy bands have alkylthiolate or amide-substituted thiophenolate ligands; the lowest energy bands are seen for complexes with benzenedithiolate ligands.…”

Section: Resultsmentioning

confidence: 95%

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.

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 95%

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.

View full text Add to dashboard Cite

show abstract

“…The model compound [MoO(SPR)4] of Hanson et al (1981) has a single broad peak at 600 nm and intense unresolved absorption at wavelengths shorter than 400 nm. The former has been assigned as the chargetransfer transition from a ligand orbital to an orbital involving the Mo=O species.…”

Section: Resultsmentioning

confidence: 99%

“…For example, in the binuclear analogues [Mo202(XR)6(OMe)]-these absorption bands arise at approx. 500 nm (Hanson et al, 1981).…”

Section: Resultsmentioning

confidence: 99%

Detection by low-temperature magnetic circular-dichroism spectroscopy of optical absorption bands due to molybdenum (V) in the form of xanthine oxidase giving the Desulpho Inhibited e.p.r. signal

Peterson¹,

Godfrey²,

Thomson³

et al. 1986

Biochemical Journal

View full text Add to dashboard Cite

The magnetic circular-dichroism (m.c.d.) spectra in the temperature range 1.5-100 K and the electronic absorption spectra at 4.2 and 295 K were measured for a number of desulpho xanthine oxidase derivatives. There were no significant differences between the absorption spectra that could be attributed to molybdenum. However, the visible-region m.c.d. spectrum of the ethanediol-treated metalloprotein (which gives rise to the Desulpho Inhibited e.p.r. signal) contained features assignable to Mo(V) absorption-bands. This is the first report of the detection of optical bands of Mo(V) in an enzyme in the presence of other chromophoric centres.

show abstract

“…(PyH) 5 4 ] were prepared by published procedures. [32,33] Pyridinium sulfate was isolated as a white solid by neutralizing sulfuric Eur. J. Inorg.…”

Section: Methodsmentioning

confidence: 99%

Dinuclear Oxomolybdate(V) Species with Oxalato and Pyridine Ligands Revisited: cis/trans Isomerization of [Mo₂O₄(η²‐C₂O₄)₂(R‐Py)₂]^2– (R‐Py = Pyridine, Alkyl‐Substituted Pyridine) in Water Evidenced by NMR Spectroscopy

et al. 2005

View full text Add to dashboard Cite

Electronic properties of thiolate compounds of oxomolybdenum(V) and their tungsten and selenium analogs. Effects of oxygen-17, molybdenum-98, and molybdenum-95 isotope substitution upon ESR spectra

Cited by 125 publications

References 7 publications

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

Detection by low-temperature magnetic circular-dichroism spectroscopy of optical absorption bands due to molybdenum (V) in the form of xanthine oxidase giving the Desulpho Inhibited e.p.r. signal

Dinuclear Oxomolybdate(V) Species with Oxalato and Pyridine Ligands Revisited: cis/trans Isomerization of [Mo₂O₄(η²‐C₂O₄)₂(R‐Py)₂]^2– (R‐Py = Pyridine, Alkyl‐Substituted Pyridine) in Water Evidenced by NMR Spectroscopy

Contact Info

Product

Resources

About

Electronic properties of thiolate compounds of oxomolybdenum(V) and their tungsten and selenium analogs. Effects of oxygen-17, molybdenum-98, and molybdenum-95 isotope substitution upon ESR spectra

Cited by 125 publications

References 7 publications

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

Detection by low-temperature magnetic circular-dichroism spectroscopy of optical absorption bands due to molybdenum (V) in the form of xanthine oxidase giving the Desulpho Inhibited e.p.r. signal

Dinuclear Oxomolybdate(V) Species with Oxalato and Pyridine Ligands Revisited: cis/trans Isomerization of [Mo2O4(η2‐C2O4)2(R‐Py)2]2– (R‐Py = Pyridine, Alkyl‐Substituted Pyridine) in Water Evidenced by NMR Spectroscopy

Contact Info

Product

Resources

About

Dinuclear Oxomolybdate(V) Species with Oxalato and Pyridine Ligands Revisited: cis/trans Isomerization of [Mo₂O₄(η²‐C₂O₄)₂(R‐Py)₂]^2– (R‐Py = Pyridine, Alkyl‐Substituted Pyridine) in Water Evidenced by NMR Spectroscopy