Kinetics of 1:1 thiocyanate (and chloride) substitution at molybdenum on the cuboidal clusters [Mo4S4(H2O)12]4+ and [Mo4S4(H2O)12]5+ in aqueous solution

Li, Yuejin; Nasreldin, Mohamed; Humanes, M.; Sykes, A. G.

doi:10.1021/ic00040a006

Cited by 38 publications

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“… On recolumning [Mo 6 SnSe 8 (H 2 O) 18 ] 8+ (particularly after storage), small amounts of [Mo 3 SnSe 4 (H 2 O) 12 ] 6+ followed by [Mo 3 Se 4 (H 2 O) 9 ] 4+ were eluted at the 1 M HCl stage. Coordination of Cl - to the Mo's results in elution of the 8+ double cube with 2 M HCl. − …”

Section: Resultsmentioning

confidence: 99%

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo₃Se₄(H₂O)₉]⁴⁺ and [W₃Se₄(H₂O)₉]⁴⁺

Hernández-Molina¹,

Dybtsev²,

Fedin³

et al. 1998

Inorg. Chem.

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The preparation and properties of Sn-containing derivatives of trinuclear MIV 3Se4 4+ incomplete cuboidal clusters [Mo3Se4(H2O)9]4+ and [W3Se4(H2O)9]4+ are described. Addition of SnII to [Mo3Se4(H2O)9]4+ gives the single-cube [Mo3SnSe4(H2O)12]6+ in 2 M Hpts (pts- = p-toluenesulfonate) and [Mo3(SnCl3)Se4(H2O)9]3+ in 2 M HCl. The structure has been determined by X-ray crystallography on (NH2Me2)6 [Mo3(SnCl3)Se4(NCS)9]·0.5H2O. The reaction of Sn metal with [Mo3Se4(H2O)9]4+ gives the first example of an Se-containing corner-shared double cube, characterized by X-ray crystallography as [Mo6SnSe8(H2O)18](pts)8·2Hpts·28H2O. The clusters [Mo3SnSe4 (H2O)12]6+ and [Mo6SnSe8(H2O)18]8+ are also characterized by the ease of elution in Dowex chromatography, ICP elemental analyses, and the stoichiometries of the oxidation with [Co(dipic)2]-. The preparation of the single-cube [W3SnSe4(H2O)12]6+ in 2 M Hpts, [W3(SnCl3)Se4 (H2O)9]3+ in 2 M HCl, is also described. Conversion of [Mo3SnSe4(H2O)12]6+ into corner-shared double-cubes [Mo6SnSe8 (H2O)18]8+, [Mo6SnSe4S4(H2O)18]8+, [Mo3W3SnSe8(H2O)18]8+, and [Mo3W3SnSe4S4(H2O)18]8+ was achieved by reductive addition of [Mo3Se4(H2O)9]4+, [Mo3S4(H2O)9]4+, [W3Se4(H2O)9]4+, and [W3S4(H2O)9]4+ using BH4 -. A similar procedure was used for the conversion of [W3Se4(H2O)9]4+ into [W6SnSe8(H2O)18]8+. Transfer of SnII is observed in the reaction of [Mo3S4(H2O)9]4+ with [Mo3SnSe4(H2O)12]6+, [W3SnSe4(H2O)12]6+, and [W3SnS4(H2O)12]6+. With the inclusion of similar reactions of [Mo3Se4(H2O)9]4+ etc., the order of affinities for SnII uptake is Mo3S4 4+ > Mo3Se4 4+ > W3Se4 4+ > W3S4 4+. The displacement of InI from [W3InSe4(H2O)12]5+ by SnII is also consistent with equilibrium processes involving dissociation of the heteroatom.

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Section: Resultsmentioning

confidence: 99%

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo₃Se₄(H₂O)₉]⁴⁺ and [W₃Se₄(H₂O)₉]⁴⁺

Hernández-Molina¹,

Dybtsev²,

Fedin³

et al. 1998

Inorg. Chem.

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“…For NCS Ϫ substitution on 87 which has four identical Mo III , the first stage of reaction gives equilibration kinetics k eq = k f [NCS Ϫ ]/4 ϩ k b , with NCS Ϫ in >10-fold excess. The second stage (independent of [NCS Ϫ ]) is assigned to isomerisation of Mo-SCN to the more stable Mo-NCS form, k isom = 3.6 × 10 Ϫ5 s Ϫ1 .…”

Section: Kinetics Studiesmentioning

confidence: 99%

Chalcogenide-bridged cuboidal clusters with M4Q4 (M = Mo, W; Q = S, Se, Te) cores

Hernández-Molina¹,

Sykes²

1999

J. Chem. Soc., Dalton Trans.

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Cuboidal cluster complexes having M 4 Q 4 cores made up of transition and main group metals (M), and non-metallic e.g. chalcogenide elements (Q), constitute a rapidly expanding area of inorganic chemistry. Extensive preparation, structural and reactivity studies have been carried out on the Group 6 metals (M ‫؍‬ Mo, W) and chalcogenide (Q ‫؍‬ S, Se, Te) clusters, and are the main focus of this perspective. The aqueous solution chemistry provides an important reference point in considering redox and other relevant properties.

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“…2 By contrast, in the case of [Mo 4 S 4 (H 2 O) 12 ] 5ϩ 1 : 1 complexing is much less favorable (K = 1.98 M Ϫ1 ). 15 According to the stoichiometry of the product the two portals of the cucurbituril are closed by the cluster cation [W 3 (CuCl)S 4 (H 2 O) 6 Cl 3 ] ϩ as shown in Fig. 1 together with an ORTEP representation of the cluster.…”

Section: New Cuboidal Clustersmentioning

confidence: 99%

Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

et al. 2004

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The triangular cluster [Mo3Se4(H2O)9]4+ reacts with Cu turnings to give a new heterometallic cuboidal cluster [Mo3CuSe4(H2O)10]4+(purple; UV/Vis lambda(epsilon): 352(3907), 509(2613)). The reaction of [Mo3Se4(H2O)9]4+ with CuCl afforded the 5+ cube [Mo3CuSe4(H2O)10]5+(red; UV/Vis lambda(epsilon): 356(5406), 500(3477)). In contrast, [W3Se4(H2O)9]4+ both with Cu and CuCl gives the 5+ cube, [W3CuSe4(H2O)10]5+(yellow-green; UV/Vis lambda(epsilon): 312(5327), 419(3256) and 628(680)). Cyclic voltammetry of [M3CuQ4(H2O)10]5+ in 2 M HCl (M = Mo, W; Q = S, Se) shows a reversible one-electron reduction wave for the Mo clusters, but no reduction occurs for the W clusters prior to H+ reduction. In HCl solutions, Cl is coordinated to the Cu site of the clusters, alongside some less extensive coordination to Mo and W, and for [W3(CuCl)S4(H2O)6Cl3]+, isolated as the supramolecular adduct with cucurbit[6]uril, [W3(CuCl)S4(H2O)6Cl3]2Cl2 x C36H36N24O12 x 12H2O, the crystal structure was determined (Cu-W 2.856(4) angstroms, W-W 2.7432(15) angstroms, Cu-Cl 2.167(13) angstroms).

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Kinetics of 1:1 thiocyanate (and chloride) substitution at molybdenum on the cuboidal clusters [Mo4S4(H2O)12]4+ and [Mo4S4(H2O)12]5+ in aqueous solution

Cited by 38 publications

References 1 publication

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo₃Se₄(H₂O)₉]⁴⁺ and [W₃Se₄(H₂O)₉]⁴⁺

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo₃Se₄(H₂O)₉]⁴⁺ and [W₃Se₄(H₂O)₉]⁴⁺

Chalcogenide-bridged cuboidal clusters with M4Q4 (M = Mo, W; Q = S, Se, Te) cores

Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

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Kinetics of 1:1 thiocyanate (and chloride) substitution at molybdenum on the cuboidal clusters [Mo4S4(H2O)12]4+ and [Mo4S4(H2O)12]5+ in aqueous solution

Cited by 38 publications

References 1 publication

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo3Se4(H2O)9]4+ and [W3Se4(H2O)9]4+

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo3Se4(H2O)9]4+ and [W3Se4(H2O)9]4+

Chalcogenide-bridged cuboidal clusters with M4Q4 (M = Mo, W; Q = S, Se, Te) cores

Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters

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Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo₃Se₄(H₂O)₉]⁴⁺ and [W₃Se₄(H₂O)₉]⁴⁺

Preparation, Structure, and Reactivity of Heterometallic Sn-Containing Single- and Double-Cube Derivatives of [Mo₃Se₄(H₂O)₉]⁴⁺ and [W₃Se₄(H₂O)₉]⁴⁺