Aryldimethylelement cations of the heavier group 14 elements. An essentially three-coordinate plumbylium ion

Abstract

The kinetically stabilized group 14 cations [RindEMe2][B(C6F5)4] (E = Si, Sn, Pb) were prepared and fully characterized (Rind = dispiro[fluorene-9,3'-(1',1',7',7'-tetramethyl-s-hydrindacen-4'-yl)-5',9''-fluorene). The deshielded heteronuclear NMR chemical shifts (δ(29Si) = 160.4, δ(119Sn)...

Hydrindacene‐Based Zinc Aryl Thiolate and Aryl Selenolate Zn(EMSFluind)2 (E=S, Se)

“…Crystals suitable for single crystal XRD were obtained by slow vapour diffusion of hexane into a solution of 1S in CDCl 3 . 1 H 13 C NMR (151 MHz, CDCl 3 ): δ = 156.05 (2,6), 152.72 (8,11,20,23), 141.07 (3,5), 140.36 (9,10,21,22), 127.81 (14,17,26,29), 127.10 (13, 18, 25, 30), 124.12 (15,16,27,28), 119.70 (12,19,24,31)…”

“…Crystals suitable for single crystal XRD were obtained by recrystallization of 1Se from toluene at 75 °C. 1 (8,11,20,23), 143.26 (3,5), 140.62 (9,10,21,22), 127.80 (14,17,26,29), 127.06 (13,18,25,30), 124.20 (15,16,27,28), 123.24 (4), 119.76 (12,19,24,31), 114.58 (1), 64.20 (7,32)…”

“…[14] In 2021, we used the M S Fluind aryl substituent for the kinetic stabilization of highly reactive phosphenium ions, [M S FluindRP] + (R=Ph, Mes), [15] which unfolded its potential for future applications. [16][17][18] In this work, we used the same M S Fluind aryl substituent for the preparation of an aryl thiol, M S FluindSH (1S), and an aryl selenol M S FluindSeH (1Se) as well as the zinc aryl thiolate Zn(SM S Fluind) 2 (2S) and the zinc aryl selenolate, Zn(SeM S Fluind) 2 (2Se).…”

Tetryliumylidene ions in synthesis and catalysis

“…[6][7][8][9][10][11][12] The heavier congeners of carbonium ions, namely tetrylium cations [R 3 E] + (E = Si, Ge, Sn, Pb), have also garnered signicant interest in recent decades attributed to their pronounced electrophilic nature, leading to various applications in catalysis and bond activation chemistry. [13][14][15][16] A related and less explored class of compounds are the tetryliumylidene ions (E = Si, Ge, Sn, Pb), which exhibit distinctive electronic properties, merging the strong electrophilicity observed in tetrylium cations with the Lewis ambiphilic character found in tetrylenes. In their idealised form, these mono-substituted cations have two vacant degenerate p orbitals and a lone pair at the E(II) centre (Fig.…”