A New Contribution Confirming the Analogy Between NO+ and Related Aryldiazo Ligands

The reaction of the cyclometalated five‐coordinate 16 electron iridium(III) complex [IrCl(H){P(tBu)2C6H4–κ2P,C}{P(tBu)2Ph}] (1) with the diazonium salt [p‐BrC6H4N2]BF4 in dichloromethane at room temperature was investigated. By spontaneous reductive elimination the iridium(I) complex salt trans‐[IrCl(N2C6H4Br‐p){(P(tBu)2)Ph}2]BF4 (2) was obtained in good yield. Therefore, this observed reaction behavior exhibits the diazonium unit as a strong π‐acceptor group and confirms furthermore the analogy between nitrosyl and aryldiazonium ligands. The new compound 2 has been characterized by standard spectroscopic methods and the molecular structure of 2 was determined by a single‐crystal X‐ray diffraction analysis (monoclinic, space group Cc, Z=4).