Neue komplexe Metallfulminate

Abstract

E Die Darstellung und IR-Spektren von iiicht explosiven, thermisch recht stabilen Tetraphenylarsonium-oder Tetraalkylammonium-Salzen der Fulminato-Komplexe [Ru(CNO)#-, [Os02(CNO)4]2 , [Rh(CN0)6] 3-, [lr(CNO)# , [Zn(CN0)4]* , [Cd(CNO)4]2 werden beschricben. Auch andere Fulminatometallat-Anionen wie [M(CNO)4]2-(M -N V , PdIl, Pt"), [M(CNO)& (M -AgI, Aul) lassen sich durch grorjvolumige Kationen stabilisieren. Die Verbindungen (R3P)zM(CN0)2 (M = Pd, Pt) sowie [AsPh4][Au(CN0)2] reagieren mit Brom oder Jod unter oxydativer Addition des Halogens zu den ,,gemischtcn" Komplexen (R3P)zM(CNO)zXz bzw. [AsPh~1[Au(CN0)2Xz] (X 1 Br, J). Rei der photochemischen Umsetzung der Hexdcarbonyle von Chrom, Molybdan und Wolfram mit dem Fulminat-Ton in THF entstehen die Difulminatotetracarbonylmetallate(O), ~s -[ M ( C O )~( C N O )~]~ , als erste Vertreter von Fulminato-Komplexen mit niedriger Oxydationszdhl des Mctalls. New Complex Metal Fulminates The preparation and infrared spectra of non explosive, thermally stable tetraphenylarsonium or tetraalkylammonium salts of the fulminato complexes [Ru(CNO),#-, [Os02(CN0)4]2-, [Rh(CNO)# , [Ir(CNO)# , [Zn(CN0)4]2-, [Cd(CNO),]Zare described. Other anions, e. g. [M(CN0)4]2-(M 2 NilI, PdIr, Ptll), [M(CN0)2]-(M = AgI, Ad) are also stabilisized by large cations. (RjP)2M(CNO)z (M = Pd, Pt) and [AsPh4][Au(CN0)2] react c2 +1 f 4 F3 t2 A 1 with bromine or iodine to give the ,,mixed" complexes (R3P)zM(CNO)zXz and [AsPh4]-[A;I(CNO)~X~], respectively (X = Br, J). Irradiation of the hexacarbonyls M(C0)h (M = Cr, Mo, W) in thc presence of fulminate ion in T H F yields difulminatotetracarbonylmetallates(O), cir-[M(C0)4(CN0)2]2-, which are the first examples of fulminato complexes containing the metal in a low oxidation state.In Fortfuhrung un5erer Arbeiten uber Metallfulminate 2) werden im folgenden neue anionische Fulminato-Komplexe der Edelmetalle sowic von Zink(l1) und Cadmium(I1) beschrieben. Das System der homogenen Fulminato-Komplcxc, deren erste Vertreter von Liebigj), Nej4) und L. Wdhlers) dargestellt wurden, wird damit erweitert und abgerundet.

The First Chemical Achievements and Publications by Justus von Liebig (1803−1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry

“…[63,64] Therefore, in the following discussion, only the most important features and the newer results will be described. In our group, [60,63] we found that fulminate complexes of transition metals can be stabilised by ''diluting'' the energy-rich metalϪfulminate groups with large cations (AsPh 4 ϩ , PPh 4 ϩ , NR 4 ϩ ) or with large neutral ligands (e.g. PPh 3 ).…”

“…Some (fulminato)metal complexes with the metal atom in a low oxidation state could be obtained from the reaction of the hexacarbonyl compounds of Cr, Mo, and W with sodium fulminate [60] as well as from the reaction of Et 4 N[W(CO) 5 Br] with AgCNO (Caution! ), [79] for example [M(CO) 5 6 ] 4Ϫ .…”

“…[24] It crystallises with 18 molecules of water, and one can speculate that its structure contains hydrogen bonds between the fulminato ligands and the water molecules (Figure 8). [18,60] Wieland described the explosive mercury complex Na 2 [Hg(CNO) 4 ]. [61] The foundations for the coordination chemistry of the fulminate ion were laid by Lothar Wöhler in Darmstadt who, between 1914 and 1929, reported (with his coworkers Martin, Weber, and Berthmann) a series of homoleptic anionic (fulminato)metal complexes, isolated as highly explosive alkali or alkaline earth metal salts.…”

“…[16,18,64a] Isomerisation MϪCϵNϪO Ǟ MϪNϭCϭO Thermal isomerisation of fulminate (at temperatures above 200°C) to the much more stable [81] isocyanate has been observed for several complexes. [60,63,67,79] As for the fulminate anion [42,43] and nitrile oxides, [22,82] the rearrangement may occur via a cyclic intermediate.…”

“…[65] Usually, these (fulminato)metal complexes were prepared from aqueous sodium fulminate solutions and transitionmetal salts, followed by the addition of tetraphenylarsonium chloride. [60,63] The aqueous solution of NaCNO can be prepared from Hg(CNO) 2 and sodium amalgam under water. [14,25,62,63] The known homoleptic anionic (fulminato)metal complexes are shown in Table 1; all correspond in their composition to cyano complexes, as it was first pointed out by Liebig [12,13,17] ( 4 ] in benzene/ethanol/water.…”