G. Becker et K. Hubler, ALKYLIDYNEPHOSPHANES AND ALKYLIDYNEARSANE S .1. [P-EQUIVALENT-TO-C-S]-[LI(DME)3]- SYNTHESIS AND STRUCTURE( ), Zeitschrift fur anorganische und allgemeine Chemie, 620(3), 1994, pp. 405-417
Citations number
89
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Zeitschrift fur anorganische und allgemeine Chemie
O,O'-Diethyl thiocarbonate and bis(tetrahydrofuran)lithium bis(trimeth
ylsilyl)phosphanide dissolved in 1,2-dimethoxyethane, react below 0-de
grees-C to give ethoxy trimethylsilane and tris(1,2-dimethoxyethane-O,
O')lithium 2lambda3-phosphaethynylsulfanide -[P=C-S]-[Li(dme)3]+ - (1a
). Apart from bis(trimethylsilyl)sulfane or carbon oxide sulfide, dark
red concentrated solutions of lambda3-phosphaalkyne 1 are also obtain
ed from reactions of carbon disulfide with bis(tetrahydrofuran)lithium
bis(trimethylsilyl)phosphanide or with the homologous lithoxy-methyli
dynephosphane (2) [1]. The ir spectrum shows two absorptions at 1762 a
nd 747 cm-1 characteristic for the P=C and C-S stretching vibrations.
The nmr parameters {delta(P-31) - 121.3; delta(C-13) 190.8 ppm; 1J(CP)
18.2 Hz} resemble much more values of diorganylamino-2lambda3-phospha
alkynes than those of -dimethoxyethane-O,O')lithoxy-methylidynephospha
ne (2a). As found by an X-ray structure analysis (P2(1))/c; a = 1192.6
(16); b = 1239.1(19); c = 1414.8(26) pm; beta = 105.91(13)degrees at -
100 +/- 3-degrees-C; Z = 4 formula units; wR = 0.064) of pale yellow c
rystals (mp. + 16-degrees-C) isolated from the reaction with O,O'-diet
hyl thiocarbonate, the solid is built up of separate [P=C-S] - and [Li
(dme)3]+ ions. Typical bond lengths and angles are: P=C 155.5(11); C-S
162.0(11); Li-O 206.4(17) to 220.3(20) pm; P=C-S 178.9(7)degrees.