New poly[(silylene)diacetylenes] and poly[(germylene)diacetylenes]: synthesis and conductive properties

Abstract

The reaction of dilithiobutadiyne (or the corresponding di-Grignard reagent) with various dichlorosilanes and dibromogermanes in THF at room temperature afforded poly[(silylene)diacetylenes] and poly[(germylene)diacetylenes], respectively, in high yields. The polymers have a regular alternating arrangement of diyne and silylene or germylene units. When they are doped with FeCl3, these polymers show conductivity values in the range 10r5-10r3 S-cm'1. The values depend greatly on the electronic character of the substituents bonded to silicon or germanium.

Tris(biphenyl‐4‐yl)silyl‐Endcapped Polyynes

“…[2] This sterically demanding endgroup places each polyyne a distance of Ͼ 8 Å from its nearest neighbor in the crystal lattice, double of that required for an intermolecular reaction to occur (Figure 2, b). [8,13] Diyne 3 shows a melting point (296-298°C) that is comparable to 1,4-bis(triphenylsilyl)-1,3-butadiyne (304°C) [14] and higher than that of 1,4-bis(methyldiphenylsilyl)-1,3-butadiyne (143°C). [13] These values are higher than those of trialkylsilyl-endcapped diynes such as 1,4-bis(TIPS)-1,3-butadiyne (98-100°C) [2] and 1,4-bis(TMS)-1,3-butadiyne (107°C).…”

Mono‐ and Dinuclear High‐Spin Half‐Sandwich Manganese(II) Complexes Containing Acetylide and TMEDA Ligands

“…Dichloromethane was distilled first from P 2 O 5 , and then prior to use from CaH 2 . Literature procedures were used to prepare the following compounds: 1,2-bis(dimethylphosphanyl)ethane (dmpe), [128] [Mn(MeC 5 H 4 ) 2 ], [102,103] [Mn(MeC 5 H 4 ) 2 (tmeda)], [105,106] Me 3 SnCϵCSiMe 3 , [129] Me 3 SiCϵ CϪCϵCH, [130] PhCϵCSnMe 3 , tBuCϵCSnMe 3 , [128] PhCϵCϪ CϵCSnMe 3 , [131] and Me 3 SnCϵCϪR"ϪCϵCSnMe 3 [RЈЈ ϭ 1,4-C 6 H 4 (CϵC) 2 , 1,3-C 6 H 4 (CϵC) 2 , 4,4Ј-C 6 H 4 C 6 H 4 (CϵC) 2 ].…”

Silyl triflates: valuable materials for the synthesis of organosilicon oligomers and polymers

“…osilanes and sodium, or organolithium compounds [3,[65][66][67]. Alkali metal/halogen exchange processes could not be present in these syntheses.…”