Preparation of a novel thallium compound of core formula, TIMo6S88+

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

“…The stoichiometry of the reaction of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ with [Fe(H 2 O) 6 ] 3+ , (eq 13), has been reported previously, with [Mo 3 S 4 (H 2 O) 9 ] 4+ as the only product.…”

“…This contrasts with the behavior in 2 M HCl solutions, where at 20 °C a 1.6 mM [Mo 6 TlS 8 (H 2 O) 18 ] 8+ solution undergoes full decay in 15 h with H 2 evolution. At 4 °C, 3 mM solutions can be stored for 3 days without full decay, consistent with the high activation energy (79 kJ mol -1 ) for reaction with H + . A possible explanation is that in Hpts solutions the cluster is protected by outer-sphere association with pts - , and formation of a network of H bonds as in crystal structures .…”

“…The Tl- and In-containing derivatives are considered first. In an earlier study on [Mo 6 TlS 8 (H 2 O) 18 ] 8+ in 2 M HCl under air-free conditions (N 2 ), a decay process believed to be the reaction with H + was reported . This has now been confirmed by GC as a reaction giving H 2 .…”

“…The double cube [Mo 6 TlS 8 (H 2 O) 18 ] 8+ is one of the most air-sensitive heterometallic derivatives known, where in air 2 M HCl solutions ∼1.5 × 10 -4 M undergo complete decay in 3 min in an open optical cell (with some shaking). At 4 °C solutions of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ under N 2 can be kept for 3 days without full decay.…”

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

“…The stoichiometry of the reaction of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ with [Fe(H 2 O) 6 ] 3+ , (eq 13), has been reported previously, with [Mo 3 S 4 (H 2 O) 9 ] 4+ as the only product.…”

“…This contrasts with the behavior in 2 M HCl solutions, where at 20 °C a 1.6 mM [Mo 6 TlS 8 (H 2 O) 18 ] 8+ solution undergoes full decay in 15 h with H 2 evolution. At 4 °C, 3 mM solutions can be stored for 3 days without full decay, consistent with the high activation energy (79 kJ mol -1 ) for reaction with H + . A possible explanation is that in Hpts solutions the cluster is protected by outer-sphere association with pts - , and formation of a network of H bonds as in crystal structures .…”

“…The Tl- and In-containing derivatives are considered first. In an earlier study on [Mo 6 TlS 8 (H 2 O) 18 ] 8+ in 2 M HCl under air-free conditions (N 2 ), a decay process believed to be the reaction with H + was reported . This has now been confirmed by GC as a reaction giving H 2 .…”

“…The double cube [Mo 6 TlS 8 (H 2 O) 18 ] 8+ is one of the most air-sensitive heterometallic derivatives known, where in air 2 M HCl solutions ∼1.5 × 10 -4 M undergo complete decay in 3 min in an open optical cell (with some shaking). At 4 °C solutions of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ under N 2 can be kept for 3 days without full decay.…”

Preparation, Structure, and Properties of the Arsenic-Containing Corner-Shared Double Cube [Mo6AsS8(H2O)18]8+: Metal−Metal Bonding and a Classification of Different Cluster Types

“…In 2.0 M HCl there is a 25% decay in 1 h, while in H(pts) there is 79% decay in 30 min (solutions were contained in an optical cell with some shaking). This relatively small change is opposite to that observed for the group 13 heteroatom double cubes and, in particular [Mo 6 TlS 8 (H 2 O) 18 ] 8+ , which is much more stable in H(pts) solutions. , No evidence was obtained for products other than the 8+ double cube in the chromatography, and in redox studies no evidence was obtained for intermediate formation of a single cube with core composition Mo 3 AsS 4 7+ , which, in view of the high charge density, is likely to be short-lived. An air-free 2 M H(pts) solution of the cluster in an optical cell, concentration ∼0.1 mM, gave only ∼3% decay in 30 min, representing maximum instability of the double cube.…”

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

“…The stoichiometry of the reaction of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ with [Fe(H 2 O) 6 ] 3+ , (eq 13), has been reported previously, with [Mo 3 S 4 (H 2 O) 9 ] 4+ as the only product.…”

“…This contrasts with the behavior in 2 M HCl solutions, where at 20 °C a 1.6 mM [Mo 6 TlS 8 (H 2 O) 18 ] 8+ solution undergoes full decay in 15 h with H 2 evolution. At 4 °C, 3 mM solutions can be stored for 3 days without full decay, consistent with the high activation energy (79 kJ mol -1 ) for reaction with H + . A possible explanation is that in Hpts solutions the cluster is protected by outer-sphere association with pts - , and formation of a network of H bonds as in crystal structures .…”

“…The Tl- and In-containing derivatives are considered first. In an earlier study on [Mo 6 TlS 8 (H 2 O) 18 ] 8+ in 2 M HCl under air-free conditions (N 2 ), a decay process believed to be the reaction with H + was reported . This has now been confirmed by GC as a reaction giving H 2 .…”

“…The double cube [Mo 6 TlS 8 (H 2 O) 18 ] 8+ is one of the most air-sensitive heterometallic derivatives known, where in air 2 M HCl solutions ∼1.5 × 10 -4 M undergo complete decay in 3 min in an open optical cell (with some shaking). At 4 °C solutions of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ under N 2 can be kept for 3 days without full decay.…”

Preparation, Structure, and Properties of the Arsenic-Containing Corner-Shared Double Cube [Mo6AsS8(H2O)18]8+: Metal−Metal Bonding and a Classification of Different Cluster Types

“…In 2.0 M HCl there is a 25% decay in 1 h, while in H(pts) there is 79% decay in 30 min (solutions were contained in an optical cell with some shaking). This relatively small change is opposite to that observed for the group 13 heteroatom double cubes and, in particular [Mo 6 TlS 8 (H 2 O) 18 ] 8+ , which is much more stable in H(pts) solutions. , No evidence was obtained for products other than the 8+ double cube in the chromatography, and in redox studies no evidence was obtained for intermediate formation of a single cube with core composition Mo 3 AsS 4 7+ , which, in view of the high charge density, is likely to be short-lived. An air-free 2 M H(pts) solution of the cluster in an optical cell, concentration ∼0.1 mM, gave only ∼3% decay in 30 min, representing maximum instability of the double cube.…”

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

“…The stoichiometry of the reaction of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ with [Fe(H 2 O) 6 ] 3+ , (eq 13), has been reported previously, with [Mo 3 S 4 (H 2 O) 9 ] 4+ as the only product.…”

“…This contrasts with the behavior in 2 M HCl solutions, where at 20 °C a 1.6 mM [Mo 6 TlS 8 (H 2 O) 18 ] 8+ solution undergoes full decay in 15 h with H 2 evolution. At 4 °C, 3 mM solutions can be stored for 3 days without full decay, consistent with the high activation energy (79 kJ mol -1 ) for reaction with H + . A possible explanation is that in Hpts solutions the cluster is protected by outer-sphere association with pts - , and formation of a network of H bonds as in crystal structures .…”

“…The Tl- and In-containing derivatives are considered first. In an earlier study on [Mo 6 TlS 8 (H 2 O) 18 ] 8+ in 2 M HCl under air-free conditions (N 2 ), a decay process believed to be the reaction with H + was reported . This has now been confirmed by GC as a reaction giving H 2 .…”

“…The double cube [Mo 6 TlS 8 (H 2 O) 18 ] 8+ is one of the most air-sensitive heterometallic derivatives known, where in air 2 M HCl solutions ∼1.5 × 10 -4 M undergo complete decay in 3 min in an open optical cell (with some shaking). At 4 °C solutions of [Mo 6 TlS 8 (H 2 O) 18 ] 8+ under N 2 can be kept for 3 days without full decay.…”

Preparation, Structure, and Properties of the Arsenic-Containing Corner-Shared Double Cube [Mo6AsS8(H2O)18]8+: Metal−Metal Bonding and a Classification of Different Cluster Types

“…In 2.0 M HCl there is a 25% decay in 1 h, while in H(pts) there is 79% decay in 30 min (solutions were contained in an optical cell with some shaking). This relatively small change is opposite to that observed for the group 13 heteroatom double cubes and, in particular [Mo 6 TlS 8 (H 2 O) 18 ] 8+ , which is much more stable in H(pts) solutions. , No evidence was obtained for products other than the 8+ double cube in the chromatography, and in redox studies no evidence was obtained for intermediate formation of a single cube with core composition Mo 3 AsS 4 7+ , which, in view of the high charge density, is likely to be short-lived. An air-free 2 M H(pts) solution of the cluster in an optical cell, concentration ∼0.1 mM, gave only ∼3% decay in 30 min, representing maximum instability of the double cube.…”