Ferrocene-Based N-Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P4.

The stable ferrocene-based N-heterocyclic silylenes fc[(N{B})2Si] (A; fc=1,1'-ferrocenylene, {B}=(HCNDipp)2B, Dipp=2,6-diisopropylphenyl) and fc[(NDipp)2Si] (B) are compared in a study focussing on their reactivity towards a range of small to moderately sized molecular substrates, viz. P4, S8, Se8, MesN3 (Mes=mesityl), RC≡CH, and RC≡CR (R=Ph, SiMe3). The Dipp-substituted congener B exhibits a more pronounced ambiphilicity and is sterically less congested than its 1,3,2-diazaborolyl-substituted relative A, in line with the higher reactivity of the former. The difference in reactivity is obviously due more to electronic than to steric reasons, as is illustrated by the fact that both A and B react with the comparatively bulky substrate MesN3 under mild conditions to afford the corresponding silanimine fc[(N{B})2Si=NMes] and fc[(NDipp)2Si=NMes], respectively. The heavier ketone analogues fc[(N{B})2Si=E] (E=S, Se, Te) are readily available from A and the corresponding chalcogen. In contrast, the reaction of the more reactive silylene B with elemental sulfur or selenium is unspecific, affording product mixtures. However, fc[(NDipp)2Si=Se] is selectively prepared from B and (Et2N)3PSe; the Te analogue is also accessible, but crystallises as head-to-tail dimer.

A complete series of N-heterocyclic tetrylenes (Si-Pb) with a 1,1'-ferrocenediyl backbone enabled by 1,3,2-diazaborolyl N-substituents.

The use of bulky 1,3,2-diazaborolyl N-substituents has allowed the synthesis of the complete series of ferrocene-based N-heterocyclic tetrylenes fc[(N{B})2E] (fc = 1,1'-ferrocenediyl, {B} = (HCNC6H3-2,6-iPr2)2B, E = Si-Pb). The silylene fc[(N{B})2Si] is inert towards NH3, CO2 or N2O under ambient conditions and thus significantly less reactive than the N-aryl homologue fc[(NC6H3-2,6-iPr2)2Si]. In accord with its higher reactivity, computational results indicate a more pronounced ambiphilicity of fc[(NC6H3-2,6-iPr2)2Si]. Our computational investigation of the model compound fc[(NBMe2)2Si] suggests that silylenes of this type may be superior to fc[(NC6H3-2,6-iPr2)2Si] in terms of ambiphilicity.

Ferrocene-Based N-Heterocyclic Plumbylenes [Fe{(η5 -C5 H4 )NSiMe2 R}2 Pb:]: Influence of the Steric Demand of the N-Substituents on Their Dimerization via C-H Activation with PbII.

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.