Chemie polyfunktioneller Liganden, 48 [1]. Synthese, Schwingungsspektren, Molekül-und Kristallstruktur eines Organocyclotriarsan-pentacarbonylchrom-Komplexes / Chemistry of Polyfunctional Ligands, 48 [1]. Synthesis, Vibrational Spectra, Molecular and Crystal Structure of an Organocyclotriarsane-pentacarbonylchromium Complex

Abstract

<jats:title>Abstract</jats:title><jats:p> The organocyclotriarsane, CH<jats:sub>3</jats:sub>C(CH<jats:sub>2</jats:sub>As)<jats:sub>3</jats:sub> (1), reacts with chromium hexacarbonyl on ultraviolet irradiation to give the complex CH<jats:sub>3</jats:sub>C(CH<jats:sub>2</jats:sub>As)<jats:sub>3</jats:sub>Cr(CO)<jats:sub>5</jats:sub> (2), in which the cyclo-triarsane is behaving as a monodentate ligand. The crystal structure of 2 has been determinated by X-ray diffraction. The monoclinic unit cell (space group P2<jats:sub>1</jats:sub>/n) contains 4 isolated molecules in a hexagonal closest packing. The mass spectrum of 2 shows the parent peak and clear fragmentation patterns. The infrared and Raman spectra are reported for 1 and 2 in the 3000-30 cm<jats:sup>-1</jats:sup> region. Most of the fundamental vibrations are assigned.</jats:p>

Chemistry of polyfunctional molecules. Part 86. Organoarsenic compounds derived from 1,3-bis(di-iodoarsino)propane with monocyclic, tricyclic, and straight-chain structures; X-ray crystal structure of 2,8,13,14-tetraoxa-1,3,7,9-tetra-arsatricyclo[7.3.1.1]tetradecane

“…

Treatment of (C,H,),As( CH,),As(C,H,),(1 ) with HI gives under elimination of benzene l,As( CH,),-Asl, (2). The reduction of (2) with sodium in tetrahydrofuran leads to the heterocyclic compound I m s l (3).

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“…Reduction of (2) with sodium in tetrahydrofuran (thf) affords the heterocyclic compound (3), which is isolated, after recrystallization from carbon disulphidedichloromethane, as deep red, air-sensitive microcrystals [equation (2)]. Surprisingly, there is I,As(CH,),AsI, + 2Na -2NaI + IAs(CH,),AsI (2) no further reduction of (2) or (3) to polyarsanes [(CH,),As,],, even on the application of an excess of sodium.…”