Rhodium(III), Palladium(II) and Rhenium(I) Complexes with 7‐(Diphenylphosphine)‐indole and ‐indolate

We present the synthesis of 7‐(diphenylphosphine)‐indole 1 ( HPinol ) as a novel mono‐ and bidentate P ‐ and N, P ‐ligand and its coordination chemical behaviour towards the d 6 ‐ and d 8 ‐transition metals rhodium(III), palladium(II) and rhenium(I). The reaction of 1 with [Cp*RhCl 2 ] 2 in a 1:2 molar ratio leads to the formation of the P ‐coordinated complex [RhCl 2 ( P –( HPinol ))] ( 2 ). In the presence of the weak base NEt 3 , HCl elimination occurs by forming the neutral amido‐phosphine chelated complex [RhCl( N, P –( Pinol ))] ( 3 ). The same P ‐ and N, P ‐coordination is observed for palladium(II), where two ligands 1 coordinate to the metal centre forming the neutral complexes [PdCl 2 ( P – HPinol ) 2 ] ( 4 ) and [Pd( N, P – Pinol ) 2 ] ( 5 ). The reaction of Re(CO) 5 Br in the presence of NEt 3 and PPh 3 delivers the amido‐phosphine complex [Re(CO) 3 PPh 3 ( N, P – Pinol )] ( 6 ). All products were characterised by multinuclear NMR spectroscopy, MS and IR spectra as well as elemental analysis. Furthermore, crystal structures of ligand 1 and all complexes 2–6 are presented.