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Synthesis and reactivity of NHC-based rhodium macrocycles
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Andrew, Rhiann and Chaplin, Adrian B. (2015) Synthesis and reactivity of NHC-based rhodium macrocycles. Inorganic Chemistry, 54 (1). pp. 312-322. doi:10.1021/ic5024828 ISSN 0020-1669.
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Official URL: http://dx.doi.org/10.1021/ic5024828
Abstract
Using a general synthetic procedure employing readily accessed terminal alkene-functionalized pro-ligands and macrocyclization by ring-closing olefin metathesis, rhodium carbonyl complexes have been prepared that contain lutidine (1a; n = 1) and pyridine (1b; n = 0) derived tridentate CNC macrocycles with dodecamethylene spacers. In solution, 1a shows temperature-invariant time-averaged C2 symmetry by 1H NMR spectroscopy (CD2Cl2, 500 MHz), whereas in the solid-state, two polymorphs can be obtained showing different conformations of the alkyl spacer about the metal–carbonyl bond (asymmetric and symmetric). In contrast, time-averaged motion of alkyl spacer in 1b can be halted by cooling below 225 K (CD2Cl2, 500 MHz), and the complex crystallizes as a dimer with an interesting unsupported Rh···Rh bonding interaction (3.2758(6) Å). Oxidative addition reactions of 1a and 1b, using MeI and PhICl2, have been studied in situ by 1H NMR spectroscopy, although pure Rh(III) adducts can be ultimately isolated only with the pyridine-based macrocyclic ligand. The lutidine backbone of 1a can be deprotonated by addition of K[N(SiMe3)2], and the resulting neutral dearomatized complex (5) has been fully characterized in solution, by variable-temperature 1H NMR spectroscopy, and in the solid state, by X-ray diffraction.
Item Type: | Journal Article | ||||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||
Journal or Publication Title: | Inorganic Chemistry | ||||||||
Publisher: | American Chemical Society | ||||||||
ISSN: | 0020-1669 | ||||||||
Official Date: | 5 January 2015 | ||||||||
Dates: |
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Volume: | 54 | ||||||||
Number: | 1 | ||||||||
Page Range: | pp. 312-322 | ||||||||
DOI: | 10.1021/ic5024828 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||
Date of first compliant deposit: | 26 May 2016 | ||||||||
Date of first compliant Open Access: | 26 May 2016 |
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