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Volumn 47, Issue 2, 2008, Pages 632-644

Coupling of CpCr(CO)3 and heterocyclic dithiadiazolyl radicals. Synthetic, X-ray diffraction, dynamic NMR, EPR, CV, and DFT studies

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EID: 38949103343     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic702128f     Document Type: Article
Times cited : (24)

References (105)
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    • We use the term redox compatible to mean species with overlapping redox stability windows, for which the driving force for an immediate electron transfer reaction is absent: Ang, C. W, Boeré, R. T, Goh, L. Y, Koh, L. L, Kuan, S. L, Tan, G. K, Yu, X. Chem. Commun. 2006, 4735-4737
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    • The unit cell of 2d contains eight monomelic F3CC 6H4CN2S2 rings in the asymmetric unit (Figure S8, each arranged to give four distinct cis-cofacial dimers, each of which has a different manifestation of steric distortion to accommodate the bulky CF3 group. These dimers associate in two zones within the lattice: in the first, four dimers aggregate around an approximate four-fold axis in a pin-wheel motif that has been observed previously for DTDA structures. In the second, six dimer pairs align side-by-side in sets of three. In each case, there are short cross-ring S⋯N interactions. In addition, there are considerably longer S⋯S and S⋯N contacts in the stacking direction. Such complexity has been seen previously in DTDA crystal structures, with two of the 45 reported neutral DTDA structures contained in the CSD (V 5.28, 2007) having the same number of monomers per equivalent posit
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    • 2 shows similar steric distortions as found in 2c, though it crystallizes with only four monomers per equivalent position in P1: Clarke, C. S.; Haynes, D. A.; Rawson, J. M.; Bond, A. D. Chem. Commun. 2003, 2774-2775. As commonly observed in such structures, the dominant local pairing into dimers - a manifestation of the Peierls distortion - prevents the long-range contacts essential for a conducting state.
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    • The existence of the 8π anion has only been demonstrated electrochemically on the time-scale of cyclic voltammetry; see ref 57
    • The existence of the 8π anion has only been demonstrated electrochemically on the time-scale of cyclic voltammetry; see ref 57.


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