γ‐Oxoisocyanid‐Komplexe von Eisen(II), Ruthenium(II), Palladium(II) und Platin(II) aus Cyano‐Komplexen und α,β‐ungesättigten Carbonylverbindungen in Gegenwart von Et 2 O–HBF 4 . Kristallstrukturanalyse von cis ‐(phen) 2 Fe[CNC(CH 3 ) 2 CH 2 C(O)CH=C(CH 3 ) 2 ] 2+ 2 (BF ‐ 4 ) 2

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 Et 2 O ‐ HBF+ Crystal Structure of cis ‐(phen) 2 Fe[CNC(CH 3 ) 2 CH 2 C(O)CH=C(CH 3 ) 2 ] 2+ 2 (BF ‐ 4 ) 2 Reactions of trans ‐(R 3 P) 2 M(CN) 2 (M = Pd, Pt), cis ‐[(phen) 2 ‐Fe(CN) 2 ], Cp(dppe)Fe(CN), and Cp(Ph 3 P) 2 Ru(CN) with several α,β‐unsaturated ketones in the presence of Et 2 O–HBF 4 yield complexes containing the γ‐oxoisocyanide ligand: trans [R 3 P) 2 M(CN–CR 1 R 2 –C(O)R 4 ) 2 ] 2+ (BF 4 ‐ ) 2 ( 5–8 ), trans ‐[(R 3 P) 2 Pt(CN)(CN‐CR 1 R 2 –CHR 3 –C(O)R 4 )] + BF 4 ‐ ( 9 ), cis [(phen 2 )]Fe(CN–CR 1 R 2 –CHR 3 –C(O)R 4 ) 2 ] 2+ (BF 4 ‐ ) 2 ( 10 ), and [CpL 2 M(CN–CR 1 R 2 ‐CHR 3 –C(O)R 4 )] * BF 4 ‐ ( 11, 12 ) (M = Fe, Ru; L = PPh 3 , 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 NaBH 4 /CeCl 3 ·6H 2 O in some cases to give complexes of γ‐hydroxyisocyanide and oxazine‐2‐ylidene ligands.