Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate.
نویسندگان
چکیده
A well-characterised 14-electron rhodium phosphine complex, [Rh(PiPr3)3][BArF4], which contains a beta-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh(PiPr3)2(PiPr2(C3H5))][BArF4]; calculations on a model system show that while C-H activation is equally accessible from the beta-CH agostic species or an alternative gamma-CH agostic isomer, subsequent beta-H-transfer can only be achieved along pathways originating from the beta-CH agostic form.
منابع مشابه
Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates† †Electronic supplementary information (ESI) available: Full details of experimental details, spectroscopic and other analytical data, X-ray crystallography, catalytic conditions, and computational studies. CCDC 1539832–1539836. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01491k
Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy2PCH2CH2PCy2)(h h-NBA)][BAr4] (NBA 1⁄4 norbornane; Ar 1⁄4 3,5-(CF3)2C6H3) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy2PCH2CH2PCy2)(alkene)x][BAr F 4] are formed. The ethene (x 1⁄4 2) comp...
متن کاملSolid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates† †Electronic supplementary information (ESI) available: Full details of experimental details, spectroscopic and other analytical data, X-ray crystallography, catalytic conditions, and computational studies. CCDC 1539832–1539836. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01491k Click here for additional data file. Click here for additional data file. Click here for additional data file.
Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy2PCH2CH2PCy2)(h h-NBA)][BAr4] (NBA 1⁄4 norbornane; Ar 1⁄4 3,5-(CF3)2C6H3) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy2PCH2CH2PCy2)(alkene)x][BAr F 4] are formed. The ethene (x 1⁄4 2) comp...
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ورودعنوان ژورنال:
- Chemical communications
دوره 2 شماره
صفحات -
تاریخ انتشار 2009