Potassium octachlorodirhenate explained

Potassium octachlorodirhenate(III) is an inorganic compound with the formula K₂Re₂Cl₈. This dark blue salt is well known as an early example of a compound featuring quadruple bond between its metal centers. Although the compound has no practical value, its characterization was significant in opening a new field of research into complexes with quadruple bonds.

Synthesis and reactions

Soviet chemists first reported K₂[Re₂Cl₈] in 1954,^[1] but it was not until 1964 that Cotton and Harris characterized the compound as featuring a short Re–Re bond, the first of its kind discovered.^{[2] [3]} The results of this classic study subsequently led to new work into other metals capable of forming metal–metal bonds, such as chromium, molybdenum, tungsten, and technetium.^{[4] [5] [6]}

A high-yield synthesis of the tetrabutylammonium salt involves treating the perrhenate salt with benzoyl chloride followed by HCl:

2 [([[n-Butyl|''n''-C₄H₉]])₄N]ReO₄ + 8 C₆H₅COCl → [(''n''-C₄H₉)₄N]₂[Re₂Cl₈] + organic products

Octachlorodirhenate(III) is a precursor to other complexes with multiply-bonded rhenium centers as the quadruple bond is quite stable and is often maintained in ligand substitution reactions. For example, upon treatment with concentrated HBr, the complex forms the analogous anion [Re₂Br₈]²⁻, which can easily be converted into other dirhenium species.^[7]

Structure and bonding

In the [Re₂Cl₈]²⁻, the Re–Re bond distance is 2.24 Å, the Re–Re–Cl bond angles are 104°, and the Cl–Re–Cl angles are 87°. The chloride ligands are fully eclipsed. Although this geometry results in repulsive interactions between the chloride ions, this conformation allows for maximum δ–δ overlap between the Re(III) centers, a factor which overrides the unfavorable chloride repulsions. The [Re₂Cl₈]²⁻ anion has a weak electrophilic character.^{[8] [9]} With the configuration, Re(III) is well suited to engage in quadruple bonding. Electrons are allocated to give the configuration σ²π⁴δ², resulting in a bond order of 4 between the rhenium centers. The brilliant color of the [Re₂Cl₈]²⁻ arises from the δ→δ* electronic transition.^[7]

References

1. Лидин Р.А., Андреева Л.Л., Молочко В.А. Константы неорганических веществ.(1954)2:161
2. Cotton. F. A.. F. A. Cotton. Harris. C. B.. The Crystal and Molecular Structure of Dipotassium Octachlorodirhenate(III) Dihydrate, K₂[Re₂Cl₈]·2H₂O. Inorg. Chem.. 1965. 4. 3. 330–333. 10.1021/ic50025a015.
3. Cotton . F. A. . March 1965 . Metal-Metal Bonding in [Re 2 X 8 ] 2- Ions and Other Metal Atom Clusters ]. Inorganic Chemistry . en . 4 . 3 . 334–336 . 10.1021/ic50025a016 . 0020-1669.
4. Hao. S.. Gambarotta. S.. Bensimon. C.. Reversible cleavage of chromium–chromium quadruple bond of [Me₈Cr₂][Li(THF)]₄ via modification of the coordination sphere of the alkali cation. Preparation and crystal structure of monomeric [Me₄Cr][Li(TMEDA)]₂. J. Am. Chem. Soc.. 1992. 114. 9. 3556–3557. 10.1021/ja00035a061.
5. Cotton. F. A.. Eglin. J. L.. Hong. B.. James. C. A.. Singlet–triplet separations measured by phosphorus-31 nuclear magnetic resonance spectroscopy. Applications to the molybdenum–molybdenum quadruple bond and to edge-sharing bioctahedral complexes. J. Am. Chem. Soc.. 1992. 114. 12. 4915–4917. 10.1021/ja00038a074.
6. Cotton. F. A.. Chen. H.. Daniels. L. M.. Feng. X.. Partial paramagnetism of the chromium–chromium quadruple bond. J. Am. Chem. Soc.. 1992. 114. 23. 8980–8983. 10.1021/ja00049a031.
7. Book: Barder. T. J.. Walton. R. A.. Inorganic Syntheses . Tetrabutylammonium Octachlorodirhenate(III) . Inorg. Synth.. 1985. 23. 116–118. 10.1002/9780470132548.ch22. 9780470132548 .
8. Shtemenko. A. V.. Kozhura. O. V.. Pasenko. A. A.. Domasevich. K. V.. New octachlorodirhenate(III) salts: solid-state manifestation for a certain conformational flexibility of the [Re₂Cl₈]²⁻ ion. Polyhedron. 2003. 22. 12. 4191–4196. 10.1016/S0277-5387(03)00288-2.
9. Book: F. A. Cotton. Cotton. F. A.. Walton. R. A.. Multiple Bonds Between Metal Atoms. registration. Oxford University Press. Oxford. 1993. 0-19-855649-7.