γ‐Oxoisocyanid‐Komplexe von Eisen(II), Ruthenium(II), Palladium(II) und Platin(II) aus Cyano‐Komplexen und α,β‐ungesättigten Carbonylverbindungen in Gegenwart von Et₂O–HBF₄. Kristallstrukturanalyse von cis‐(phen)₂Fe[CNC(CH₃)₂CH₂C(O)CH=C(CH₃)₂]²⁺₂(BF^‐₄)₂

Abstract

Pseudohalogeno Metal Compounds, LXXIII. ‐ γ‐Oxoisocyanide Complexes of Iron(II), Ruthenium(II), Palladium(II), and Platinum(I1) from Cyano Complexes and α,β‐Unsaturated Carbonyl Compounds in the Presence of Et2O ‐ HBF+ Crystal Structure of cis‐(phen)2Fe[CNC(CH3)2CH2C(O)CH=C(CH3)2]2+2(BF‐4)2 Reactions of trans‐(R3P)2M(CN)2 (M = Pd, Pt), cis‐[(phen)2‐Fe(CN)2], Cp(dppe)Fe(CN), and Cp(Ph3P)2Ru(CN) with several α,β‐unsaturated ketones in the presence of Et2O–HBF4 yield complexes containing the γ‐oxoisocyanide ligand: trans [R3P)2M(CN–CR1R2–C(O)R4)2]2+(BF4‐)2 (5–8), trans ‐[(R3P)2Pt(CN)(CN‐CR1R2–CHR3–C(O)R4)]+ BF4‐ (9), cis [(phen2)]Fe(CN–CR1R2–CHR3–C(O)R4)2]2+(BF4‐)2 (10), and [CpL2M(CN–CR1R2‐CHR3–C(O)R4)]*BF4‐ (11, 12) (M = Fe, Ru; L = PPh3, 1/2 dppe). The compounds were characterized by their spectroscopic data, 10g by X‐ray crystallography. The carbonyl function of the coordinated ligands could be reduced by NaBH4/CeCl3·6H2O in some cases to give complexes of γ‐hydroxyisocyanide and oxazine‐2‐ylidene ligands.