Preparation and Properties of Group 13 (Ga, In, Tl) Heterometallic Single and Corner-Shared Double Cube Derivatives of [Mo₃S₄(H₂O)₉]⁴⁺ and Related Studies

Abstract

New routes are described for the preparation of cuboidal complexes [Mo(3)InS(4)(H(2)O)(12)](5+), [Mo(3)GaS(4)(H(2)O)(12)](5+), and [Mo(6)InS(8)(H(2)O)(18)](8+) from the incomplete cuboidal [Mo(3)S(4)(H(2)O)(9)](4+). A comparison of the aqueous solution properties of the single cubes, [Mo(3)GaS(4)(H(2)O)(12)](5+) and [Mo(3)InS(4)(H(2)O)(12)](5+), and the double cubes, [Mo(6)InS(8)(H(2)O)(18)](8+) and [Mo(6)TlS(8)(H(2)O)(18)](8+), the total listing of group 13 derivatives, is reported. The single cube [Mo(3)InS(4)(H(2)O)(12)](5+) can be quantitatively converted into the double cube by reductive (H(3)PO(2) or BH(4)(-)) addition of [Mo(3)S(4)(H(2)O)(9)](4+). The double cubes are O(2) sensitive, much more so in HCl than Hpts (pts(-) = p-toluenesulfonate), and are oxidized by H(+) in HCl solutions with the formation of H(2) (detected by gas chromatography). The single cubes are less reactive in air, and are only oxidized by H(+) at higher ( approximately 4 M) levels. Stoichiometry measurements with [Co(dipic)(2)](-) and [Fe(H(2)O)(6)](3+) as 1e(-) oxidants were used to confirm charges on the clusters. In the absence of reduction potentials, rate constants for outer-sphere [Co(dipic)(2)](-) oxidations give a measure of redox properties. Oxidation of [Mo(6)InS(8)(H(2)O)(18)](8+) with [Co(dipic)(2)](-) provides a route back to the single cube [Mo(3)InS(4)(H(2)O)(12)](5+). Properties of [W(3)InS(4)(H(2)O)(12)](5+) and [Mo(6)InO(2)S(6)(H(2)O)(18)](8+) obtained from [W(3)S(4)(H(2)O)(9)](4+) and [Mo(3)OS(3)-(H(2)O)(9)](4+) are also considered. The single cube [W(3)InS(4)(H(2)O)(12)](5+) is >10(3) times more reactive with [Co(dipic)(2)](-) than [Mo(3)InS(4)(H(2)O)(12)](5+), consistent with reducing properties W > Mo. No evidence was obtained in these studies for [Mo(3)TlS(4) (H(2)O)(12)](5+), [Mo(6)GaS(8)(H(2)O)(18)](8+), or the recently proposed 6+ analogue of [Mo(3)GaS(4)(H(2)O)(12)](5+).

Preparation and properties of the heterometallic cube [Mo3CdS4(H2O)12]4+ and the reaction with H+

“…Coordination of Cl Ϫ to [Cd(H 2 O) 6 ] 2ϩ is more favourable by an order of magnitude as compared to other transition metal ions. 19 The oxidation of heterometallic derivatives of [Mo 3 S 4 -(H 2 O) 9 ] 4ϩ with H ϩ has been observed previously, 17 but is a relatively rare occurrence confined to group 12 and 13 heteroatoms. Evolution of H 2 gas has been monitored in all cases by gas chromatography.…”

“…Evolution of H 2 gas has been monitored in all cases by gas chromatography. 17 ] 8ϩ occurs in two steps (eqn. 8 and eqn.…”

“…9). 17 The reaction of the In ϩ aqua ion with H ϩ gives a first-order dependence on [H ϩ ]. 20,21 In all these reactions, the behaviour observed contrasts with the dominant [H ϩ ] 2 rate law term observed for eqn.…”

Preparation and properties of the heterometallic cube [Mo3CdS4(H2O)12]4+ and the reaction with H+

“…Coordination of Cl Ϫ to [Cd(H 2 O) 6 ] 2ϩ is more favourable by an order of magnitude as compared to other transition metal ions. 19 The oxidation of heterometallic derivatives of [Mo 3 S 4 -(H 2 O) 9 ] 4ϩ with H ϩ has been observed previously, 17 but is a relatively rare occurrence confined to group 12 and 13 heteroatoms. Evolution of H 2 gas has been monitored in all cases by gas chromatography.…”

“…Evolution of H 2 gas has been monitored in all cases by gas chromatography. 17 ] 8ϩ occurs in two steps (eqn. 8 and eqn.…”

“…9). 17 The reaction of the In ϩ aqua ion with H ϩ gives a first-order dependence on [H ϩ ]. 20,21 In all these reactions, the behaviour observed contrasts with the dominant [H ϩ ] 2 rate law term observed for eqn.…”

Cobalt(II) and Cobalt(III) Dipicolinate Complexes: Solid State, Solution, and in Vivo Insulin-like Properties

“…The K 2 [Co(dipic) 2 ] complex has more absorption maxima with the major two at 460 and 583 nm. These signals are assigned to d-d transitions analogous with the d-d transitions observed in, for example, [Co(H 2 O) 6 ] 2+ at about 530 nm. 38 The extinction coefficients of these complexes are about 30-fold less than the Co(III) complex at 16 and 17 cm -1 M -1 .…”

Preparation, Structure, and Reactivity of Ge-Containing Heterometallic Cube Derivatives of [M3E4(H2O)9]4+ (M = Mo, W; E = S, Se)

“… No reverse reaction was observed on addition of a 20-fold excess of Ge II to [W 3 InS 4 (H 2 O) 12 ] 5+ (0.05 mM). The UV−vis spectrum of W 3 InS 4 5+ , and the ability of Sn II to displace In I , has been reported previously . Relative affinities for [W 3 S 4 (H 2 O) 9 ] 4+ are therefore Sn II > In I > Ge II .…”

Preparation and properties of the heterometallic cube [Mo3CdS4(H2O)12]4+ and the reaction with H+

“…Coordination of Cl Ϫ to [Cd(H 2 O) 6 ] 2ϩ is more favourable by an order of magnitude as compared to other transition metal ions. 19 The oxidation of heterometallic derivatives of [Mo 3 S 4 -(H 2 O) 9 ] 4ϩ with H ϩ has been observed previously, 17 but is a relatively rare occurrence confined to group 12 and 13 heteroatoms. Evolution of H 2 gas has been monitored in all cases by gas chromatography.…”

“…Evolution of H 2 gas has been monitored in all cases by gas chromatography. 17 ] 8ϩ occurs in two steps (eqn. 8 and eqn.…”

“…9). 17 The reaction of the In ϩ aqua ion with H ϩ gives a first-order dependence on [H ϩ ]. 20,21 In all these reactions, the behaviour observed contrasts with the dominant [H ϩ ] 2 rate law term observed for eqn.…”

Cobalt(II) and Cobalt(III) Dipicolinate Complexes: Solid State, Solution, and in Vivo Insulin-like Properties

“…The K 2 [Co(dipic) 2 ] complex has more absorption maxima with the major two at 460 and 583 nm. These signals are assigned to d-d transitions analogous with the d-d transitions observed in, for example, [Co(H 2 O) 6 ] 2+ at about 530 nm. 38 The extinction coefficients of these complexes are about 30-fold less than the Co(III) complex at 16 and 17 cm -1 M -1 .…”

Preparation, Structure, and Reactivity of Ge-Containing Heterometallic Cube Derivatives of [M3E4(H2O)9]4+ (M = Mo, W; E = S, Se)

“… No reverse reaction was observed on addition of a 20-fold excess of Ge II to [W 3 InS 4 (H 2 O) 12 ] 5+ (0.05 mM). The UV−vis spectrum of W 3 InS 4 5+ , and the ability of Sn II to displace In I , has been reported previously . Relative affinities for [W 3 S 4 (H 2 O) 9 ] 4+ are therefore Sn II > In I > Ge II .…”

Preparation and properties of the heterometallic cube [Mo3CdS4(H2O)12]4+ and the reaction with H+

“…Coordination of Cl Ϫ to [Cd(H 2 O) 6 ] 2ϩ is more favourable by an order of magnitude as compared to other transition metal ions. 19 The oxidation of heterometallic derivatives of [Mo 3 S 4 -(H 2 O) 9 ] 4ϩ with H ϩ has been observed previously, 17 but is a relatively rare occurrence confined to group 12 and 13 heteroatoms. Evolution of H 2 gas has been monitored in all cases by gas chromatography.…”

“…Evolution of H 2 gas has been monitored in all cases by gas chromatography. 17 ] 8ϩ occurs in two steps (eqn. 8 and eqn.…”

“…9). 17 The reaction of the In ϩ aqua ion with H ϩ gives a first-order dependence on [H ϩ ]. 20,21 In all these reactions, the behaviour observed contrasts with the dominant [H ϩ ] 2 rate law term observed for eqn.…”

Cobalt(II) and Cobalt(III) Dipicolinate Complexes: Solid State, Solution, and in Vivo Insulin-like Properties

“…The K 2 [Co(dipic) 2 ] complex has more absorption maxima with the major two at 460 and 583 nm. These signals are assigned to d-d transitions analogous with the d-d transitions observed in, for example, [Co(H 2 O) 6 ] 2+ at about 530 nm. 38 The extinction coefficients of these complexes are about 30-fold less than the Co(III) complex at 16 and 17 cm -1 M -1 .…”

Preparation, Structure, and Reactivity of Ge-Containing Heterometallic Cube Derivatives of [M3E4(H2O)9]4+ (M = Mo, W; E = S, Se)

“… No reverse reaction was observed on addition of a 20-fold excess of Ge II to [W 3 InS 4 (H 2 O) 12 ] 5+ (0.05 mM). The UV−vis spectrum of W 3 InS 4 5+ , and the ability of Sn II to displace In I , has been reported previously . Relative affinities for [W 3 S 4 (H 2 O) 9 ] 4+ are therefore Sn II > In I > Ge II .…”