Ligand Substitution Reactions at the Nickel of [Mo3NiS4(H2O)10]4+ with Two Water Soluble Phosphines, CO, Br−, I−, and NCS− and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo3(NiL)S4(H2O)9]4+

Saysell, D. M.; Borman, Christopher D.; Kwak, Chee‐Hun; Sykes, A. G.

doi:10.1021/ic950562x

Cited by 37 publications

(35 citation statements)

References 36 publications

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“…[11] Stopped-flow experiments on the kinetics of the substitution of water by chloride or thiocyanate [13,14] confirmed the existence of non-equivalent H 2 O ligands, as substitution reactions at d sites are faster. [15] More importantly from the point of view of the present work, each one of the resolved kinetic steps in these substitution reactions corresponds to a reaction at equivalent sites on the three metal centres with statistically controlled kinetics. [14] As those classical works by the group of Sykes were carried out by monitoring the kinetics at a single wavelength, there is the possibility that some of the kinetic steps were unresolved because of minor changes at that wavelength.…”

Section: Introductionmentioning

confidence: 83%

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M₃Q₄ (M=Mo, W; Q=S, Se) Cuboidal Clusters

Algarra

Fernández‐Trujillo

Basallote

2012

Chemistry A European J

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For many years it has been known that the nine water molecules in [M(3)Q(4)(H(2)O)(9)](4+) cuboidal clusters (M = Mo, W; Q = S, Se) can be replaced by entering ligands, such as chloride or thiocyanate, and kinetic studies carried out mainly on the substitution of the first water molecule at each metal centre reveal that the reaction at the three metal centres occurs with statistical kinetics; that is, a single exponential with a rate constant corresponding to the reaction at the third centre is observed instead of the expected three-exponential kinetic trace. Such simplification of the kinetic equations requires the simultaneous fulfilment of two conditions: first that the three consecutive rate constants are in statistical ratio, and second that the metal centres behave as independent chromophores. The validity of those simplifications has been checked for the case of the reaction of [Mo(3)S(4)(H(2)O)(9)](4+) with Cl(-) by using DFT and TD-DFT theoretical calculations. The results of those calculations are in agreement with the available experimental information, which indicates that the H(2)O ligands trans to the μ-S undergo substitution much faster than those trans to the μ(3)-S. Moreover, the energy barriers for the substitution of the first water molecule at the three metal centres are close to each other, the differences being compatible with the small changes in the numerical values of the rate constants required for observation of statistical kinetics. TD-DFT calculations lead to calculated electronic spectra, which are in reasonable agreement with those experimentally measured, but the calculations do not indicate that the three metal centres behave as independent chromophores, although the mathematical conditions required for simplification of the kinetic traces to a single exponential are reasonably well fulfilled at certain wavelengths. A re-examination of the kinetics of the reaction by using global fitting procedures yields results, which are compatible with statistical kinetics, although an alternative interpretation in which substitution only occurs at a single metal centre under reversible conditions is also possible.

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Section: Introductionmentioning

confidence: 83%

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M₃Q₄ (M=Mo, W; Q=S, Se) Cuboidal Clusters

Algarra

Fernández‐Trujillo

Basallote

2012

Chemistry A European J

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“…20 The rate constants of these reactions are 119 L mol -1 s -1 for X = PTA and 58 L mol -1 s -1 for X = TPPTS 3-, which are substantially smaller that those for the palladium clusters. Therefore, our data on the reactions of nickel and palladium clusters with hydrophosphoryl compounds agree well with the data 20 on the reactions of these clusters with phosphines.…”

Section: (M´pph 3 )S 4 (Mecp) 3 ] + 21 and [Mo 3 (M´pph 3 )S 4 CL 4 (mentioning

confidence: 90%

Stabilization of tautomeric forms P(OH)3 and HP(OH)2 and their derivatives by coordination to palladium and nickel atoms in heterometallic clusters with the Mo3MQ4 4+ core (M = Ni, Pd; Q = S, Se)

et al. 2005

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The cluster aqua complexes [Mo 3 (MCl)Q 4 (H 2 O) 9 ] 3+ (M = Pd or Ni) in hydrochloric acid solutions induce isomerization of the hydrophosphoryl compounds (HO) 2 P(O)H, (HO)P(O)H 2 , PhP(O)(OH)H, and Ph 2 P(O)H into the hydroxo tautomers P(OH) 3 , HP(OH) 2 , PhP(OH) 2 , and Ph 2 P(OH), which are stabilized by coordination of the phosphorus atom to the Pd or Ni atoms. The reactions were studied by 31 P NMR and UV Vis spectroscopy. The kinetics of the reactions of phosphorous acid with [Mo 3 (PdCl)Q 4 (H 2 O) 9 ] 3+ was investigated by spectropho tometry. The [Mo 3 (Pd(PhP(OH) 2 ))S 4 (H 2 O) 2 Cl 7 ] 3-complex was isolated as a supramolecular adduct with cucurbit[8]uril, and the [Mo 3 (Ni(P(OH) 3 ))S 4 (H 2 O) 8 Cl] 3+ complex was isolated as an adduct with cucurbit[6]uril. The structures of both compounds were established by X ray diffraction analysis.

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“…[1][2][3][4] In the last 20 years, the reactivity and kinetics of ligand-exchange [5][6][7][8][9] and isomerisation reactions [10][11][12] at the M' centres in cuboidal M 3 M'S 4 clusters (M = Mo, W; M' = Fe, Ru, Co, Ni, Pd, Pt, Cu) have been intensely studied. The M 3 M'S 4 units remain intact in all cases, thus indicating the robustness of these units.…”

Section: Introductionmentioning

confidence: 99%

Unprecedented Solvent‐Assisted Reactivity of Hydrido W₃CuS₄ Cubane Clusters: The Non‐Innocent Behaviour of the Cluster‐Core Unit

Algarra¹,

Feliz²,

Fernández‐Trujillo³

et al. 2009

Chemistry A European J

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Registro de acceso restringido Este recurso no está disponible en acceso abierto por política de la editorial. No obstante, se puede acceder al texto completo desde la Universitat Jaume I o si el usuario cuenta con suscripción. Registre d'accés restringit Aquest recurs no està disponible en accés obert per política de l'editorial. No obstant això, es pot accedir al text complet des de la Universitat Jaume I o si l'usuari compta amb subscripció. Restricted access item This item isn't open access because of publisher's policy. The full--text version is only available from Jaume I University or if the user has a running suscription to the publisher's contents.

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Ligand Substitution Reactions at the Nickel of [Mo₃NiS₄(H₂O)₁₀]⁴⁺ with Two Water Soluble Phosphines, CO, Br⁻, I⁻, and NCS⁻ and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo₃(NiL)S₄(H₂O)₉]⁴⁺

Cited by 37 publications

References 36 publications

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M₃Q₄ (M=Mo, W; Q=S, Se) Cuboidal Clusters

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M₃Q₄ (M=Mo, W; Q=S, Se) Cuboidal Clusters

Stabilization of tautomeric forms P(OH)3 and HP(OH)2 and their derivatives by coordination to palladium and nickel atoms in heterometallic clusters with the Mo3MQ4 4+ core (M = Ni, Pd; Q = S, Se)

Unprecedented Solvent‐Assisted Reactivity of Hydrido W₃CuS₄ Cubane Clusters: The Non‐Innocent Behaviour of the Cluster‐Core Unit

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Ligand Substitution Reactions at the Nickel of [Mo3NiS4(H2O)10]4+ with Two Water Soluble Phosphines, CO, Br−, I−, and NCS− and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo3(NiL)S4(H2O)9]4+

Cited by 37 publications

References 36 publications

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M3Q4 (M=Mo, W; Q=S, Se) Cuboidal Clusters

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M3Q4 (M=Mo, W; Q=S, Se) Cuboidal Clusters

Stabilization of tautomeric forms P(OH)3 and HP(OH)2 and their derivatives by coordination to palladium and nickel atoms in heterometallic clusters with the Mo3MQ4 4+ core (M = Ni, Pd; Q = S, Se)

Unprecedented Solvent‐Assisted Reactivity of Hydrido W3CuS4 Cubane Clusters: The Non‐Innocent Behaviour of the Cluster‐Core Unit

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Ligand Substitution Reactions at the Nickel of [Mo₃NiS₄(H₂O)₁₀]⁴⁺ with Two Water Soluble Phosphines, CO, Br⁻, I⁻, and NCS⁻ and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo₃(NiL)S₄(H₂O)₉]⁴⁺

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M₃Q₄ (M=Mo, W; Q=S, Se) Cuboidal Clusters

A DFT and TD‐DFT Approach to the Understanding of Statistical Kinetics in Substitution Reactions of M₃Q₄ (M=Mo, W; Q=S, Se) Cuboidal Clusters

Unprecedented Solvent‐Assisted Reactivity of Hydrido W₃CuS₄ Cubane Clusters: The Non‐Innocent Behaviour of the Cluster‐Core Unit