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• W4376226150 abstract "Ferrocene-based N-heterocyclic plumbylenes fc[(NSiMe2 R)2 Pb:] (1; fc=1,1'-ferrocenylene) are easily accessible by transamination from [(Me3 Si)2 N]2 Pb and the corresponding 1,1'-diaminoferrocene derivatives fc(NHSiMe2 R)2 . They may form unconventional dimers 2 by a process, which causes the cleavage of a cyclopentadienyl C-H bond and the formation of a Pb-C and an N-H bond. The monomer-dimer equilibrium (2 1⇆2) has been addressed experimentally and computationally. It critically depends on the steric demand of the N-substituents SiMe2 R, which has been varied systematically by using homologues with aliphatic (R=methyl, ethyl, isopropyl, tert-butyl) and aromatic units (R=phenyl, mesityl, ferrocenyl). Even in the sterically least congested case (R=methyl), dimerization is only slightly exergonic. It eventually becomes prohibitively endergonic with increasingly larger substituents and is thus not observed for R=tert-butyl, mesityl, and ferrocenyl. R=phenyl represents a borderline case, where the dimer is still detectable in the equilibrium mixture, albeit as a very minor component, in accord with the slightly endergonic Gibbs free energy change calculated for its formation. Addition of 4-dimethylaminopyridine (DMAP) to the monomer-dimer equilibrium mixtures cleanly affords the corresponding adducts [1(DMAP)], irrespective of the equilibrium composition." @default.
• W4376226150 created "2023-05-13" @default.
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• W4376226150 date "2023-05-17" @default.
• W4376226150 modified "2023-10-11" @default.
• W4376226150 title "Ferrocene‐Based N‐Heterocyclic Plumbylenes [Fe{(η⁵‐C₅H₄)NSiMe₂R}₂Pb:]: Influence of the Steric Demand of the <i>N</i>‐Substituents on Their Dimerization via C−H Activation with Pb^II" @default.
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• W4376226150 doi "https://doi.org/10.1002/asia.202300266" @default.
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