The stabilisation of indium (1) in acetonitrile

Headridge, J. B.; Pletcher, Derek

doi:10.1016/0020-1650(67)80068-0

Cited by 22 publications

(11 citation statements)

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“…Indium powder (150 mesh), anhydrous acetonitrile, and anhydrous silver trifluoromethanesulfonate were Aldrich products. Indium(I) solutions were prepared under argon by a modification 7 of the procedure of Headridge,8b and their In(I) content was estimated iodometrically as described . Aqueous In(I) solutions in O 2 -free water for kinetic experiments were stable for over 5 h at 25 °C in the absence of added electrolyte and in 0.13 M LiClO 4 but decomposed perceptibly (17% loss in 5 min) in 0.06 M HClO 4 .…”

Section: Methodsmentioning

confidence: 99%

“…The recent preparation of aqueous In(I) solutions having much greater concentrations (10 -2 −10 -3 M) of this reductant than those previously recorded (and exhibiting substantially improved stability) has made it possible to examine the behavior of this hypovalent center in inorganic redox transformations. Reactions with complexes of the type (NH 3 ) 5 Co III (Lig) entail a slow formation of the metastable state In II , which is then rapidly oxidized to In III .…”

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confidence: 99%

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Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)¹

Chandra

Gould

1997

Inorg. Chem.

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Aqueous solutions of the hypovalent state indium(I) react with oxidants of the type [(NH(3))(5)Ru(III)(Lig)](3+), in which the sixth ligand, "Lig", is devoid of groups allowing inner-sphere bridging. Reaction stoichiometry conforms to the relationship In(I) + 2Ru(III) --> In(III) + 2Ru(II). Kinetic profiles are consistent with a two-step sequence initiated by the formation of metastable In(II), which then reacts rapidly with Ru(III). Rate constants for the rate-determining steps in this series (k(Ru,In) values) are proportional to those for reductions of the corresponding (NH(3))(5)Co(III) oxidants with V(2+)(aq), Cr(2+)(aq), Eu(2+)(aq), and U(3+)(aq), even though, for each comparison, no metal center is common to the two series chosen. This implies that changes in DeltaG()(redox) arising from substitution of one N-donor ligand for another are nearly independent of the metal centers involved in the net transfer. The rate for the reduction of (NH(3))(6)Ru(3+), considered in the framework of the Marcus model, leads to an estimated rate constant of 10(-9) M(-1) s(-1) for electron self-exchange in the system In(2+/+). This value lies well below the range characteristic of the most usual aqua-substituted cationic couples, suggesting a more severe H(2)O-metal bond contraction in going from the uni- to the dipositive cation.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)¹

Chandra

Gould

1997

Inorg. Chem.

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“…Materials. Indium(I) solutions were prepared and handled under argon using a modification 8 of the procedure of Headridge, and their In(I) content was estimated iodimetrically as described . Titanium(III) solutions were prepared, stored, and standardized as described by Ram …”

Section: Methodsmentioning

confidence: 99%

Electron Transfer. 135. Pendant Carbonyl Groups in the Mediation of the Reactions of Indium(I) with Bound Ruthenium(III)¹

1997

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Reductions, using In(I)(aq) and Ti(III)(aq), of (NH(3))(5)Ru(III) derivatives of pyridines having carbonyl-bearing substituents (-CONH(2), -COOCH(3), and -COC(6)H(5)) yield the corresponding (NH(3))(5)Ru(II) complexes. Reactions with Ti(III) are kinetically straightforward, exhibit only slight responses to structural alteration, and give no indication of inner-sphere mediation involving the carbonyl group. Kinetic profiles for In(I) reductions of the 3-CONH(2), 3-COOCH(3), and 3-COC(6)H(5)-substituted complexes (in the range [H(+)] = 0.030-0.15 M) begin with a nearly linear section, with rates independent of [In(I)], but show curvature during the later stages of reaction. These profiles are consistent with a reaction sequence in which the predominant carbonyl form of the oxidant is hydrated to a more reactive gem-diol form (>C=O + H(2)O right harpoon over left harpoon >C(OH)(2)), which undergoes reduction by In(I), yielding the observed Ru(II) product and In(II). The latter is then rapidly consumed by a second unit of Ru(III). Rate constants for the hydration step giving optimal fit to the experimental curves are 6 x 10(-4) s(-1) (for the 3-CONH(2) complex) and 1.3 x 10(-3) s(-1) (for the 3-COOCH(3) oxidant). Lower limits for the rate of attack by In(I) on the active forms of the oxidants are estimated as 10(3.3)-10(4.6) M(-1) s(-1), about 10(2)-10(3) times are rapid as the reduction of the unsubstituted pyridine complex. Our results suggest the utilization, by In(I), of a hydroxyl-bridged path featuring the sequence In(I)-OH-C(OH)-py in these reductions, a path which is overshadowed, in the case Ti(III) reactions, by a more facile outer-sphere process.

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“…The observed kinetic picture, in conjunction with the 2 : 1 stoichiometry, is consistent with a two-step reaction sequence [eqn. (3)], proceeding through the metastable state In", which reacts with Co' II much more rapidly than does In'. The rate constants for the initial step would then be 1/2 of the tabulated values.…”

Section: Mecnmentioning

confidence: 99%

“…In111 + 2 CO" Reactions at 25 "C in H20-MeCN (300 : 1); p = 0Conversions were monitored at the low-energy absorption maxima of the cobalt(Ir1) oxidants. Rate constants pertain to the disappearance of CoIII; if the overall reaction is taken to proceed by eqn (3),. values of k for the initial electron transfer from In1 would be 1/2 of the tabulated values.…”

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Convenient preparation and improved stability of aqueous indium(I) solutions used in electron transfer reactions

Chandra¹,

Gould²

1996

Chem. Commun.

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Solutions 0.27 mol dm-3 in I d , prepared by treatment of indium amalgam with silver triflate in dry acetonitrile, are stable for more than 5 days in the absence of oxygen and may be diluted 300-fold with water to give InI(aq) solutions which are stable for over 5 h; kinetic patterns for reactions of [Co(NH&X]2+ (X = Cl-, Br-, I-, HC204-) with In' point to a pair of consecutive 1 e transactions, the first (slower) of which is predominantly inner sphere.

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The stabilisation of indium (1) in acetonitrile

Cited by 22 publications

References 2 publications

Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)¹

Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)¹

Electron Transfer. 135. Pendant Carbonyl Groups in the Mediation of the Reactions of Indium(I) with Bound Ruthenium(III)¹

Convenient preparation and improved stability of aqueous indium(I) solutions used in electron transfer reactions

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The stabilisation of indium (1) in acetonitrile

Cited by 22 publications

References 2 publications

Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)1

Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)1

Electron Transfer. 135. Pendant Carbonyl Groups in the Mediation of the Reactions of Indium(I) with Bound Ruthenium(III)1

Convenient preparation and improved stability of aqueous indium(I) solutions used in electron transfer reactions

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Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)¹

Electron Transfer. 134. Reduction of Bound Ruthenium(III) by Indium(I)¹

Electron Transfer. 135. Pendant Carbonyl Groups in the Mediation of the Reactions of Indium(I) with Bound Ruthenium(III)¹