ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Pseudohalogeno Metal Compounds, LXIV. Reactions of Cyano Complexes of Iron(II), Ruthenium(II), Osmium(II), and Platinum(II) with α,β-Unsaturated Carbonyl Compounds or Ketones in the Presence of Acids: γ-Oxoisocyanide Complexes. X-Ray Structure of {Fe[CNC(CH3)2CH2C(O)CH3]6} 2+(BF4-2)2The reactions of H4[M(CN)6, [M(CN)6]4- and. [(Ph3P)2Pt(CNH)2]2+ with mesityl oxide or diacetone alcohol in the presence of HBF4 · Et2O give the γ-oxoisocyanide complexes{M[C≡N—C(CH3)2CH2C(O)CH3]6}2+(BF4-)2 (1a: M = Fe; 2: M = Ru; 3: M = Os) und {Ph3P)2Pt[C≡N—C(CH3)2CH2C(O)CH3]2}2+(BF4--)2) (4, respectively. Analogous iron(II) complexes {Fe[C≡N—C(R1)(R2)C(H)(R3)C(O)R4]6}2+(BF4-)2 (1c - f) have been obtained by treatment of [Fe(CN)6]4- with various ketones which can undergo aldol condensation (ethyl methyl ketone, isobutyl methyl ketone, acetophenone, cyclohexanone), and HBF4. The formation of the cationic isocyanide complexes proceeds by addition of the carbenium ion to the nucleophilic N-atom of the cyanide ligands. The compounds have been characterized by spectroscopic data, 1a by an X-ray structural determination. Derivatives of all six carbonyl groups in 1a have been prepared with 2,4-dinitrophenylhydrazine and hydroxylamine. The carbonyl groups of 1a can be reduced by NaBH4/CeCl3.
Notes:
Die Umsetzungen von H4M(CN)6oder [M(CN)6]4- bzw. [Ph3P)2Pt(CNH)2]2+ mit Mesityloxid oder Diacetonalkohol in Gegenwart von HBF4 · Et2O liefern die γ-Oxoisocyanid-Komplexe {M[C≡N—C(CH3)2(CH2C(O)CH3]6}2+(BF4-)2 (1a: M = Fe; 2: M = Ru; 3: M = Os) und {Ph3P)2Pt[C≡N—C(CH3)2CH2C(O)CH3]2}2+(BF4-)2) (4). Weitere Eisen(II)-Komplexe dieser Art, {Fe[C≡N—C(R1)(R2)C(H)(R3)C(O)R4]6}2+(BF4-)2 (1c - f), werden aus [Fe(CN)6]4-, verschiedenen Ketonen, die zur Aldol-Kondensation befähigt sind (Ethylmethylketon, Isobutylmethylketon, Acetophenon, Cyclohexanon), und HBF4 erhalten. Die Bildung dieser kationischen Isocyanid-Komplexe erfolgt durch Addition des Carbenium-Ions an das nucleophile N-Atom der Cyanid-Liganden. Die Verbindungen werden spektroskopisch, 1a durch eine Röntgenstrukturanalyse charakterisiert. Eine Derivatisierung aller sechs Carbonylgruppen von 1 a gelingt mit 2,4-Dinitrophenylhydrazin und Hydroxylamin. Die Carbonylgruppen von 1a lassen sich mit NaBH4/CeCl3 zur Alkoholfunktion reduzieren.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19851180604
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