Template‐Controlled Formation of an [11]ane‐P 2 C NHC Macrocyclic Ligand at an Iron(II) Template

Complex [Fe(η 5 ‐C 5 H 5 )(η 6 ‐PhMe)]PF 6 reacts with 1,2‐bis[bis(2‐fluorophenyl)phosphanyl]benzene ( 2 ) in acetonitrile under irradiation for 6 h to give complex [Fe(η 5 ‐C 5 H 5 )( 2 )(CH 3 CN)]PF 6 ([ 3 ]PF 6 ). Reaction of [ 3 ]PF 6 with 1 equiv. of 2‐azidoethyl isocyanide ( 4 ) yields complex [Fe(η 5 ‐C 5 H 5 )( 2 )( 4 )]X ([ 5 ]X) (X = Br, PF 6 ). Staudinger reaction with PPh 3 at the azido function followed by hydrolysis of the iminophosphorane with HBr yields compound [ 6 ]X (X = Br – , PF 6 – ) with an NH,NH‐stabilized NHC ligand. The facially coordinated NH,NH‐stabilized NHC and the fluorinated diphosphane ligands were linked by N , N′ ‐deprotonation of the NHC and nucleophilic attack of the nitrogen atoms at two C–F bonds, which gave – after anion exchange with NH 4 PF 6 – complex [ 1 ]PF 6 bearing the macrocyclic [11]ane‐P 2 C NHC ligand.