The exchange reaction between rhenium hexafluoride and boron trichloride and enthalpies of formation of rhenium pentachloride and rhenium hexafluoride

Burgess, John; Fraser, C. J. W.; Haigh, I.; Peacock, R. D.

doi:10.1039/dt9730000501

Cited by 12 publications

(8 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…All the neutral hexafluorides, MF 6 (M = W to Pt), are well-characterized species. ,, In contrast, of the neutral 5d hexachlorides, only WCl 6 is well established. ReCl 6 has been claimed, but the characterization has been disputed . Our calculations predict that PtF 6 has the highest electron affinity of all the hexahalometalates studied here.…”

Section: Discussionmentioning

confidence: 68%

Stabilization of High Oxidation States in Transition Metals. 2.¹ WCl₆ Oxidizes [WF₆]^-, but Would PtCl₆ Oxidize [PtF₆]^-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF₆]^z versus [MCl₆]^z (M = Ta to Pt; z = 0, 1−, 2−)

Macgregor¹,

Moock

1998

Inorg. Chem.

View full text Add to dashboard Cite

The trends in redox potentials for isovalent series of 5d hexafluoro- and -chlorometalates, [MX6]0/- and [MX6]-/2- (M = Ta to Pt; X = F, Cl), are compared, including the previously unpublished electrochemistry of [IrF6]2-. For a given series, the trend in redox data can be understood in terms of the core charge of the metal and interelectronic terms. However, there is a marked convergence of the electrochemical redox potentials for isovalent series of [MF6] z / z -1 and [MCl6] z / z -1 (z = 0, 1−) complexes. Thus, while the oxidation potential of [TaF6]2- is 1.6 V lower than that of [TaCl6]2-, the oxidation potential of [IrF6]2- is only 0.5 V lower than that of [IrCl6]2-. The redox data correlate well with computed electron affinities of MX6 and [MX6]- derived from density functional calculations. A fragmentation approach is adopted to analyze the electrochemical trends in terms of the properties of the metal center and trends in the metal−halide bonding. The observed convergence in redox data for isovalent [MX6] z / z -1 (x = F, Cl; z = 0, 1−) series is rationalized in terms of the ability of the halide arrays to stabilize the two metal oxidation states involved. The ability of the chloride array to stabilize the higher metal oxidation state increases more rapidly along the third row transition metals than does that of the fluoride array. This counteracts the effects of metal core charge to produce the observed convergence. The computational results indicate that, for the later metals in their highest oxidation states, the redox-active orbital becomes increasingly halide based. In view of this, the stability of the neutral hexahalides with respect to the reductive elimination of X2 was studied, and the results suggest that OsCl6 and IrCl6 are more likely to be stable as novel hexachlorides than PtCl6.

show abstract

Section: Discussionmentioning

confidence: 68%

Stabilization of High Oxidation States in Transition Metals. 2.¹ WCl₆ Oxidizes [WF₆]^-, but Would PtCl₆ Oxidize [PtF₆]^-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF₆]^z versus [MCl₆]^z (M = Ta to Pt; z = 0, 1−, 2−)

Macgregor¹,

Moock

1998

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…The reaction of ReFg with BCI3 has recently been found to give only ReClg and fluoride chlorides of boron. 222 The synthesis of ReClg in a low-temperature matrix does not seem to have been attempted.…”

Section: Complexesmentioning

confidence: 99%

Recent advances in the chemistry of rhenium

Rouschias¹

1974

Chem. Rev.

226

View full text Add to dashboard Cite

“…In binären Verbindungen mit Chlor wird hingegen maximal ReCl 5 gebildet, und ein postuliertes ReCl 6 hat sich ebenfalls nur als ReCl 5 herausgestellt 1. 2 Die Oxidationsstufe 6 tritt allerdings in der ternären Verbindung ReOCl 4 auf 3. Die einzige bisher bekannte Rhenium(VII)‐Chlor‐Verbindung war ReO 3 Cl, das sich nach mehreren Methoden auch in größeren Mengen herstellen lässt 4.…”

Section: Methodsunclassified

Rheniumtrichloriddioxid, ReO₂Cl₃

Supeł¹,

Seppelt²

2006

Angewandte Chemie

View full text Add to dashboard Cite

Neues vom Rhenium: Die einzige bisher bekannte Rhenium‐Chlor‐Verbindung mit Rhenium in der Oxidationsstufe 7 war ReO3Cl, und die Elementkombination AO2Cl3 (A=Nichtmetall oder Metall) war völlig unbekannt. Nun gelang die Synthese des ersten Dioxidtrichlorids: ReO2Cl3. Diese Verbindung liegt im Kristall als Chlor‐verbrücktes Dimer und in Lösung als Monomer vor (Abbildung: Molekülstruktur des Dimers; rot Re, blau O, grün Cl).

show abstract

The exchange reaction between rhenium hexafluoride and boron trichloride and enthalpies of formation of rhenium pentachloride and rhenium hexafluoride

Cited by 12 publications

References 0 publications

Stabilization of High Oxidation States in Transition Metals. 2.¹ WCl₆ Oxidizes [WF₆]^-, but Would PtCl₆ Oxidize [PtF₆]^-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF₆]^z versus [MCl₆]^z (M = Ta to Pt; z = 0, 1−, 2−)

Stabilization of High Oxidation States in Transition Metals. 2.¹ WCl₆ Oxidizes [WF₆]^-, but Would PtCl₆ Oxidize [PtF₆]^-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF₆]^z versus [MCl₆]^z (M = Ta to Pt; z = 0, 1−, 2−)

Recent advances in the chemistry of rhenium

Rheniumtrichloriddioxid, ReO₂Cl₃

Contact Info

Product

Resources

About

The exchange reaction between rhenium hexafluoride and boron trichloride and enthalpies of formation of rhenium pentachloride and rhenium hexafluoride

Cited by 12 publications

References 0 publications

Stabilization of High Oxidation States in Transition Metals. 2.1 WCl6 Oxidizes [WF6]-, but Would PtCl6 Oxidize [PtF6]-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF6]z versus [MCl6]z (M = Ta to Pt; z = 0, 1−, 2−)

Stabilization of High Oxidation States in Transition Metals. 2.1 WCl6 Oxidizes [WF6]-, but Would PtCl6 Oxidize [PtF6]-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF6]z versus [MCl6]z (M = Ta to Pt; z = 0, 1−, 2−)

Recent advances in the chemistry of rhenium

Rheniumtrichloriddioxid, ReO2Cl3

Contact Info

Product

Resources

About

Stabilization of High Oxidation States in Transition Metals. 2.¹ WCl₆ Oxidizes [WF₆]^-, but Would PtCl₆ Oxidize [PtF₆]^-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF₆]^z versus [MCl₆]^z (M = Ta to Pt; z = 0, 1−, 2−)

Stabilization of High Oxidation States in Transition Metals. 2.¹ WCl₆ Oxidizes [WF₆]^-, but Would PtCl₆ Oxidize [PtF₆]^-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF₆]^z versus [MCl₆]^z (M = Ta to Pt; z = 0, 1−, 2−)

Rheniumtrichloriddioxid, ReO₂Cl₃