The metalation of toluene (PhCH3) with a 1: 1 mixtureof n-BuLi/MOtBu (M = K, Rb) at ambient temperature affords orange-red powders of benzylpotassium or benzylrubidium. On addition of N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA) the precipitates dissolve to give burgundy-red solutions, from which needles of [PhCH2K-PMDTA.O.5PhCH3ln (1) or [PhCH2RbPMDTA], (2) areobtained. X-ray analysis reveals that 1 incorporates half a molecule of toluene per asymmetric unit. In both 1 and 2, the 73 and 76 interaction of one M+ cation with two benzyl fragments gives rise to the formation of polymeric chains. The coordination sphere of the cations is completed by one chelating triamine ligand. M O calculations predict multihapto metal carbon interactions to become more important from Li to Cs and substantiate the solid-state results. Ab initio calculations on three different polymers suggest that the array present in the crystal structure is the most stable. The gated decoupled 13C NMR spectrum of 1 in THF-dg solution reveals a IJ(I3C,lH) coupling constant for the benzylic carbon atom which may be interpreted in terms of a mainly planar configuration of the CH2-group in solution.

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Articles you may be interested inCrystal orbital calculation of coupled Hartree-Fock dynamic (hyper)polarizabilities for prototype π -conjugated polymers Erratum: "Assessment of conventional density functional schemes for computing the polarizabilities and hyperpolarizabilities of conjugated oligomers: An ab initio investigation of polyacetylene chains" [J.Assessment of conventional density functional schemes for computing the polarizabilities and hyperpolarizabilities of conjugated oligomers: An ab initio investigation of polyacetylene chains

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