“…Our spectrum contains a corresponding band at 326 nm. The bands in the spectra of 2 and 6 have been assigned as S → M charge transfer transitions. , Although there is an apparent discrepancy in relative intensities for 2 , perhaps due in part to different solvents, we conclude that species generated in aqueous solution and our preparations by two methods are the same. 5 UV−vis absorption spectra (λ max (ε M )) of monosulfido species in acetonitrile solutions.…”
Reactions of [MO(4)](2)(-) (M = Mo, W) with certain carbon and silicon electrophiles were investigated in acetonitrile in order to produce species of potential utility in the synthesis of analogues of the sites in the xanthine oxidoreductase enzyme family. Silylation of [MoO(4)](2)(-) affords [MoO(3)(OSiPh(3))](1)(-), which with Ph(3)SiSH is converted to [MoO(2)S(OSiPh(3))](1)(-). Reaction with (Ph(3)C)(PF(6))/HS(-) yields the tetrahedral monosulfido species [MO(3)S](2)(-), previously obtained only from the aqueous system [MO(4)](2)(-)/H(2)S. Dithiolene chelate rings are readily introduced upon reaction with 1,2-C(6)H(4)(SSiMe(3))(2), leading to the square pyramidal trioxo complexes [MO(3)(bdt)](2)(-), a previously unknown dithiolene molecular type. Further ring insertion occurs upon reaction of [WO(3)(bdt)](2)(-) with 1,2-C(6)H(4)(SSiMe(3))(2), giving [WO(2)(bdt)(2)](2)(-). Related reactions occur with [ReO(4)](1)(-). Treatment with 1 equiv of (Me(3)Si)(2)S produces [ReO(3)S](1)(-); with 3 equiv of 1,2-C(6)H(4)(SSiMe(3))(2), [ReO(bdt)(2)](1)(-) is obtained with concomitant Re(VII) --> Re(V) reduction. X-ray structures are reported for [MO(3)S](z)(-) (M = Mo, W, z = 2; M = Re, z = 1), [MO(3)(bdt)](2)(-), and [WO(2)(OSiPh(3))(bdt)](1)(-), a silylation product of [WO(3)(bdt)](2)(-). [MoO(3)(bdt)](2)(-) is related to the site of inactive sulfite oxidase, and [WO(2)(OSiPh(3))(bdt)](1)(-) should closely approximate the metric features of the [(dithiolene)MoO(2)(OH)] site in inactive aldehyde/xanthine oxidoreductase. This work provides convenient syntheses of known and new derivatives of tetraoxometalates, among which is entry to a unique class of oxo-monodithiolene complexes.
“…Our spectrum contains a corresponding band at 326 nm. The bands in the spectra of 2 and 6 have been assigned as S → M charge transfer transitions. , Although there is an apparent discrepancy in relative intensities for 2 , perhaps due in part to different solvents, we conclude that species generated in aqueous solution and our preparations by two methods are the same. 5 UV−vis absorption spectra (λ max (ε M )) of monosulfido species in acetonitrile solutions.…”
Reactions of [MO(4)](2)(-) (M = Mo, W) with certain carbon and silicon electrophiles were investigated in acetonitrile in order to produce species of potential utility in the synthesis of analogues of the sites in the xanthine oxidoreductase enzyme family. Silylation of [MoO(4)](2)(-) affords [MoO(3)(OSiPh(3))](1)(-), which with Ph(3)SiSH is converted to [MoO(2)S(OSiPh(3))](1)(-). Reaction with (Ph(3)C)(PF(6))/HS(-) yields the tetrahedral monosulfido species [MO(3)S](2)(-), previously obtained only from the aqueous system [MO(4)](2)(-)/H(2)S. Dithiolene chelate rings are readily introduced upon reaction with 1,2-C(6)H(4)(SSiMe(3))(2), leading to the square pyramidal trioxo complexes [MO(3)(bdt)](2)(-), a previously unknown dithiolene molecular type. Further ring insertion occurs upon reaction of [WO(3)(bdt)](2)(-) with 1,2-C(6)H(4)(SSiMe(3))(2), giving [WO(2)(bdt)(2)](2)(-). Related reactions occur with [ReO(4)](1)(-). Treatment with 1 equiv of (Me(3)Si)(2)S produces [ReO(3)S](1)(-); with 3 equiv of 1,2-C(6)H(4)(SSiMe(3))(2), [ReO(bdt)(2)](1)(-) is obtained with concomitant Re(VII) --> Re(V) reduction. X-ray structures are reported for [MO(3)S](z)(-) (M = Mo, W, z = 2; M = Re, z = 1), [MO(3)(bdt)](2)(-), and [WO(2)(OSiPh(3))(bdt)](1)(-), a silylation product of [WO(3)(bdt)](2)(-). [MoO(3)(bdt)](2)(-) is related to the site of inactive sulfite oxidase, and [WO(2)(OSiPh(3))(bdt)](1)(-) should closely approximate the metric features of the [(dithiolene)MoO(2)(OH)] site in inactive aldehyde/xanthine oxidoreductase. This work provides convenient syntheses of known and new derivatives of tetraoxometalates, among which is entry to a unique class of oxo-monodithiolene complexes.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
