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Organorhenium chemistry
Organorhenium chemistry describes the compounds with Re−C bonds. Because rhenium is a rare element, relatively few applications exist, but the area has been a rich source of concepts and a few useful catalysts.
Rhenium exists in ten known oxidation states from −3 to +7 except −2, and all but Re(−3) are represented by organorhenium compounds. Most are prepared from salts of perrhenate and related binary oxides. The halides, e.g., ReCl5 are also useful precursors as are certain oxychlorides.
A noteworthy feature of organorhenium chemistry is the coexistence of oxide and organic ligands in the same coordination sphere.
Dirhenium decacarbonyl is a common entry point to other rhenium carbonyls. The general patterns are similar to the related manganese carbonyls. It is possible to reduce this dimer with sodium amalgam to Na[Re(CO)5] with rhenium in the formal oxidation state −1. Bromination of dirhenium decacarbonyl gives bromopentacarbonylrhenium(I), then reduced with zinc and acetic acid to pentacarbonylhydridorhenium:
Bromopentacarbonylrhenium(I) is readily decarbonylated. In refluxing water, it forms the triaquo cation:
With tetraethylammonium bromide Re(CO)5Br reacts to give the anionic tribromide:
One of the first transition metal hydride complexes to be reported was (C5H5)2ReH. A variety of half-sandwich compounds have been prepared from (C5H5)Re(CO)3 and (C5Me5)Re(CO)3. Notable derivatives include the electron-precise oxide (C5Me5)ReO3 and (C5H5)2Re2(CO)4.
Rhenium forms a variety of alkyl and aryl derivatives, often with pi-donor coligands such as oxo groups. Well known is methylrhenium trioxide ("MTO"), CH3ReO3 a volatile, colourless solid, a rare example of a stable high-oxidation state metal alkyl complex. This compound has been used as a catalyst in some laboratory experiments. It can be prepared by many routes, a typical method is the reaction of Re2O7 and tetramethyltin:
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Organorhenium chemistry
Organorhenium chemistry describes the compounds with Re−C bonds. Because rhenium is a rare element, relatively few applications exist, but the area has been a rich source of concepts and a few useful catalysts.
Rhenium exists in ten known oxidation states from −3 to +7 except −2, and all but Re(−3) are represented by organorhenium compounds. Most are prepared from salts of perrhenate and related binary oxides. The halides, e.g., ReCl5 are also useful precursors as are certain oxychlorides.
A noteworthy feature of organorhenium chemistry is the coexistence of oxide and organic ligands in the same coordination sphere.
Dirhenium decacarbonyl is a common entry point to other rhenium carbonyls. The general patterns are similar to the related manganese carbonyls. It is possible to reduce this dimer with sodium amalgam to Na[Re(CO)5] with rhenium in the formal oxidation state −1. Bromination of dirhenium decacarbonyl gives bromopentacarbonylrhenium(I), then reduced with zinc and acetic acid to pentacarbonylhydridorhenium:
Bromopentacarbonylrhenium(I) is readily decarbonylated. In refluxing water, it forms the triaquo cation:
With tetraethylammonium bromide Re(CO)5Br reacts to give the anionic tribromide:
One of the first transition metal hydride complexes to be reported was (C5H5)2ReH. A variety of half-sandwich compounds have been prepared from (C5H5)Re(CO)3 and (C5Me5)Re(CO)3. Notable derivatives include the electron-precise oxide (C5Me5)ReO3 and (C5H5)2Re2(CO)4.
Rhenium forms a variety of alkyl and aryl derivatives, often with pi-donor coligands such as oxo groups. Well known is methylrhenium trioxide ("MTO"), CH3ReO3 a volatile, colourless solid, a rare example of a stable high-oxidation state metal alkyl complex. This compound has been used as a catalyst in some laboratory experiments. It can be prepared by many routes, a typical method is the reaction of Re2O7 and tetramethyltin: