Synthesis and properties of stable 2-metallanaphthalenes of heavier group 14 elements

Abstract

The first stable neutral stannaaromatic compound, 2-stannanaphthalene , was synthesized by taking advantage of an extremely bulky and efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt). The molecular structure and aromaticity of were discussed on the basis of X-ray crystallographic analysis, NMR, UV-vis, and Raman spectroscopy, cyclic voltammetry, and theoretical calculations. 2-Germanaphthalene , which has a framework similar to that of , was synthesized for comparison, and systematic elucidation was made for the properties of 2-metallanaphthalene systems containing a heavier group 14 element (Si, Ge, or Sn).

[4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2SnL]+: An NHC‐Stabilized Organotin(II) Cation and Related Derivatives

“…[3b] Notably, carbene-stabilized germanium cations of the types [(NHC) 3 Ge] 2 + and [(NHC) 2 GeCl] + (NHC = DCA C H T U N G T R E N N U N G (iPrNCMe) 2 ) have been reported. [22] The C(1)-Sn-C(27) angle of 101.2(1)8 in 1 clearly shows the SnÀC Carbene interaction is not of the stannene-type, [23] which is consistent with the Lewis basic nature of the IPr ligand. [22] The C(1)-Sn-C(27) angle of 101.2(1)8 in 1 clearly shows the SnÀC Carbene interaction is not of the stannene-type, [23] which is consistent with the Lewis basic nature of the IPr ligand.…”

“…They are smaller than the analogous angles in the parent organotin(II) chloride RSnCl (152.01(6)8) [20c] and the corresponding triorganotin(IV) cation [RSnPh 2 ] + (159.01(9)8). [22] The C(1)-Sn-C(27) angle of 101.2(1)8 in 1 clearly shows the SnÀC Carbene interaction is not of the stannene-type, [23] which is consistent with the Lewis basic nature of the IPr ligand. The angle is, however, as result of steric hindrance, larger than the C(1)-Sn-N(1) angle of 91.73(8)8 in 2, which, in turn, is similar to the C(1)-Sn-Cl(1) angle in RSnCl (94.23(6)8).…”

Exploring the effectiveness of different Lewis pair combinations in caged structures for the catalysis of ammonia borane dehydrogenation: a DFT study

“…46 C 5 Ge aromatic structures have also been reported, with bulky substituent groups present to stabilize the complex. [47][48][49][50][51] Ge-C or GeQGe double bonded complexes have also been reported. 47,52,53 It is also noteworthy that amino-germyne complexes have been synthesized recently.…”

Cycloaddition Reactions of Kinetically Stabilized 9‐Silaanthrancene with Polycyclic Aromatic Hydrocarbons

“…[1] As part of our ongoing research projects in the area of novel aromatic compounds, we have already succeeded in the synthesis of several stable and neutral metallaaromatic systems containing a silicon, germanium, or tin atom, which constitute the heavier analogues of benzene, naphthalene, anthracene, and phenanthrene, by the application of a sterically bulky 2,4,6-trisA C H T U N G T R E N N U N G [bis(trimethyl-A C H T U N G T R E N N U N G silyl)methyl]phenyl protecting group (Tbt). [2][3][4] Studies on their structural and spectroscopic properties together with theoretical calculations indicate that these metallaaromatic compounds have high aromaticity comparable to those of the parent hydrocarbon compounds. Unlike the parent hy-drocarbon compounds, however, due to their metallene (M= C) or metalladiene (M=CÀC=C) moiety (M = Si, Ge, or Sn), they show high reactivity in the addition reactions with protic reagents, elemental oxygen, sulfur, and selenium, and compounds bearing an unsaturated bond.…”