NDLI: Synthesis of a rhodium(I) germyl complex: a useful tool for C–H and C

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Ahrens, Theresia Herrmann, Roy Braun, Thomas Ahrens, Mike Braun, Beatrice
Description	Author Affiliation: Ahrens T ( Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Straße 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.)
Abstract	The dihydrido germyl complex $cis,fac-[Rh(GePh_{3})(H)_{2}(PEt_{3})_{3}]$ (2) was synthesized by an oxidative addition of $HGePh_{3}$ at $[Rh(H)(PEt_{3})_{3}]$ (1). Treatment of 2 with neohexene generated the rhodium(I) germyl complex $[Rh(GePh_{3})(PEt_{3})_{3}]$ (3). Alternatively, treatment of the methyl complex $[Rh(CH_{3})(PEt_{3})_{3}]$ (4) with $HGePh_{3}$ furnished at room temperature also 3. Low-temperature NMR measurements revealed an initial formation of the oxidative addition product $fac-[Rh(GePh_{3})(H)(CH_{3})(PEt_{3})_{3}]$ (5), which transforms into the intermediate complex $[Rh(GePh_{3})(H)(CH_{3})(PEt_{3})_{2}]$ (6) by dissociation of a triethylphosphine ligand. The reductive elimination of methane and coordination of $PEt_{3}$ afforded the germyl complex 3. Treatment of 3 with CO gave the biscarbonyl complex $[Rh(GePh_{3})(CO)_{2}(PEt_{3})_{2}]$ (7). The molecular structures of the complexes 2, 3 and 7 were determined by X-ray crystallography. The germyl complex 3 reacted with 2,3,5,6-tetrafluoropyridine or pentafluorobenzene to furnish the C–H activation products $[Rh(4-C_{5}NF_{4})(PEt_{3})_{3}]$ (8) and $[Rh(C_{6}F_{5})(PEt_{3})_{3}]$ (9), respectively. The reaction of 3 with hexafluorobenzene or perfluorotoluene gave selectively the C–F activation products 9 and $[Rh(4-C_{6}F_{4}CF_{3})(PEt_{3})_{3}]$ (10). Treatment of 3 with pentafluoropyridine resulted in the formation of the C–F activation products 8 and $[Rh(2-C_{5}NF_{4})(PEt_{3})_{3}]$ (11) in a 1:10 ratio. The two isomeric activation compounds $[Rh\{(E)-CF=CF(CF_{3})\}(PEt_{3})_{3}]$ (12) and $[Rh\{(Z)-CF=CF(CF_{3})\}(PEt_{3})_{3}]$ (13) were obtained in a 3:1 ratio by reaction of 3 with hexafluoropropene. On exposure to oxygen the highly air sensitive complex 12 reacts to yield the peroxido-bridged dirhodium complex $[Rh\{(E)-CF=CF(CF_{3})\}(μ–κ^{1}:η^{2}-O_{2})(PEt_{3})_{2}]_{2}$ (14). The molecular structure of 14 was determined by X-ray crystallography.
ISSN	14779226
Issue Number	11
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-03-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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