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- W2146390010 abstract "The (Bu3P)2Ni complexes of 9-alkyl and 9,10-dialkylanthracene (alkyl = Me, Et) were prepared and their structural and dynamic properties studied. It was found that in the 9-substituted systems the nickel is bound ν2 to C(3)–C(4) of the anthracene. Based on chemical shift analysis of similar systems [e.g. (Bu3P)2Ni-anthracene and (depe)Ni-anthracene] and spin saturation transfer experiments, it was determined that the 9,10-dialkyl anthracenes are not ν4 complexes (as appears from the NMR spectra) but ν2 complexes in which two isomeric (however, chemically identical) structures equilibriate rapidly. The dynamic behavior of the systems was studied using spin saturation transfer and line shape analysis VT-NMR techniques. It was found that in all the systems under study the (Bu3P)2Ni moiety rearranges between the two terminal rings of the anthracene. In the 9-substituted systems (3) there are two rearrangement pathways: an intermolecular one (with ΔH‡ of ca. 8 kcal mol−1 and a negative ΔS‡) and an intermolecular rearrangement with ΔH‡ of ca. 20 kcal mol−1 and a positive ΔS‡. The 9,10 disubstituted anthracene complexes (4) show two intermolecular rearrangements, each of them with similar activation parameters as the intra- and intermolecular rearrangements of 3. All the rearrangements are of a kinetic first order. On the basis of these data a rearrangement mechanism is proposed. Using magnetization transfer to a hidden partner it was found that a methyl destabilises the Ni-anthracene bond by 1.2–3 kcal mol−1, probably because of steric effects." @default.
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- W2146390010 date "1996-05-01" @default.
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- W2146390010 title "Inter- vs. intramolecular rearrangement of a (Bu3)2 Ni moiety in its 9-alkyl and 9,10-dialkyl anthracene complexes. Limiting conditions and isomer stabilities" @default.
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- W2146390010 doi "https://doi.org/10.1016/0022-328x(95)06104-5" @default.
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