Organoindium Compounds of Lower Oxidation States
The product obtained from the reaction of In(CH2Si(CH3)3)3 with NaH was first considered to be an organoindium(I) derivative with the formula Na(In(CH2Si(CH3)3)2) [2]. Later investigations by the same researchers [4] demonstrated that they had synthesized
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[1] [2] [3] [4] [5] [6] [7]
Schmidbaur, H.; FuLLer, H.-J. (Chem Ber. 107 [1974] 3674/9). Schmidbaur, H.; Fuller, H.-J. (Chem Ber. 110 [1977] 3528/35). Schmidbaur, H.; FuLLer, H.-J. (Ger. 2701143 [1978]; C.A. 90 [1979] No. 23243). Yamamoto, Y. (BuLL. Chem. Soc. Japan 56 [1983]1772/4). Yamamoto, Y. (BuLL. Chem. Soc. Japan 57 [1984] 2835/8). Yamamoto, Y. (Bull. Chem. Soc. Japan 60 [1987]1189/91). Yamamoto, Y.; Numasaki, Y.; Murakami, M. (Nippon Kaguku Kaishi 1985 625/8 from C.A. 103 [1985] No. 47866). [8] Annan, T. A.; Tuck, o. G.; Khan, M. A.; Peppe, C. (OrganometaLLics 10 [1991]2159/66).
12 Organoindium Compounds of Lower Oxidation States The product obtained from the reaction of In(CH 2Si(CH 3)3)3 with NaH was first considered to be an organoindium(l) derivative with the formula Na[ln(CH 2Si(CH 3bh] [2]. Later investigations by the same researchers [4] demonstrated that they had synthesized a mixture of Na[ln(CH 2Si(CH 3b)4] and Na[ln(CH2Si(CH3bbH] (thus, In!II); see also Table 64, No. 12. Also mentioned is one In! compound of the InR type, InC g H7 0 3 (Formula I on p. 376) and its adduct Cl 3B' InCg H7 0 3 (dec. at 145°C); they are insoluble, and the structures of these compounds are unknown [1]. 12.1
Organoindium{II) Compounds
In this chapter the only isolable compound containing an In-In bond is described. CH3InBr
Indium vapor and CH 3Br were co-condensed in an argon matrix at both 12 and 77 K. It was postulated that In had inserted into the C-Br bond, as evidenced by Q(CH 3) absorption bands at 744 cm- 1 (12 K) and 738 cm- 1 (77 K) in the IR reflectance spectrum. Above 77 K the In and CH 3Br reactants were reformed. When the reaction was conducted with C0 3Br, the result was complicated but not comparable; the differences among AI, Ga, and In were discussed [3]. [In{ CH(Si(CH 3h)2}212
This compound was prepared from a pentane suspension of In 2Br 4.2 (CH 3)2NCH 2CH 2N(CH 3i2 with 4 equivalents of Li[CH(Si(CH 3bh] in O(C 2H 5 h at - 60°C. The mixture was allowed to warm (metallic In separates at about - 20 00) and was stirred an additional 45 min at room temperature. After removing the solvent, the residue was taken up in pentane and precipitated by cooling to - 30 °C; orange-red crystals, monomeric in benzene, dec. 154°C, 54% yield. A second product of the disproportionation, In{CH(Si(CH 3U2b (see p. 80), was isolated from the mother liquor [5]. The NMR spectra were run in C 6 0 6 (8 values in ppm). (CHin). 13C NMR: 5.0 (CH 3Si), 28.2 (CHin) [5].
1H
NMR: 0.27 (s, CH 3Si), 0.90
The vibration frequencies are given in cm -1. IR (solid): 1255 sh, 1250 s 8(CH 3), 1022 s 8 (CH), 916 m, 898 m, 845 vs, 783 w, 768 s, 750 s, 725 sh, aLL Q(CH 3Si), 682 m, 660 s, 595 m, aLL v(SiC 3), 479 s v as (lnC 2), 460 m v S (lnC 2), 410 w, 331 w 8(SiC 3). Raman (C 6 H6 ): 798 w, 765 w, 748 vw, 729 vw, aLL Q(CH 3Si); 681 m, 665 m v(SiC 3), 485 sh v as (lnC 2), 463 s v S (lnC 2), 342 w 8(SiC 3), 246 m cm- 1 unassigned; v(ln-In) not observed [5]. Gmelin Handbook In-Org. Camp. 1
J. Weidlein, In Organoindium Compounds © Springe
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