Observation of Cationic Transition Metal–Alkane Complexes with Moderate Stability in Hydrofluorocarbon Solution
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资源简介：
In
seeking to create more-stable transition metal–alkane
complexes, we generated cationic alkane complexes of the type [(HEB)Re(CO)2(alkane)][Al(ORf)4] (HEB
= η6-hexaethylbenzene; alkane = cyclopentane
(16) or pentane (17–19); ORf = perfluoro-tert-butoxy) via photolysis
of the precursor complex [(HEB)Re(CO)3][Al(ORf)4] (15) in the presence of the added
alkane. The alkane complexes were generated in a hydrofluorocarbon
(HFC) solvent, most often CF3CH2CF3, which is capable of simultaneously dissolving the ionic complex 15 and a small amount of alkane at low temperature (183 K).
Use of the HFC solvent in tandem with the highly fluorinated, solubilizing,
weakly coordinating [Al(ORf)4]− anion overcomes the technical difficulty of combining ionic species
with alkanes in solution without the solvent molecules rapidly displacing
the bound alkane ligand, as the alkanes bind in preference to the
HFCs to the organometallic fragments employed in this study.
The [(HEB)Re(CO)2(alkane)]+ complexes
are more long-lived than the corresponding neutral alkane complexes
[(HEB)W(CO)2(alkane)] and [CpRe(CO)2(alkane)] (Cp = η5-cyclopentadienyl),
with samples of [CpRe(CO)2(cyclopentane)] decaying
significantly more rapidly than [(HEB)Re(CO)2(alkane)]+ when present in the same solution. Intramolecular exchange
of the methylene group bound to the metal within the cyclopentane
ligand in 16 was observed at 212 K, with the 1,2 shifts
appearing to be faster than 1,3 shifts.
创建时间：
2016-02-12
