Phosphinoindenyl and phosphazidoindenyl complexes of lanthanum and samarium: synthesis, characterisation, and hydroamination catalysis.

The phosphinoindenyl rare-earth metal complexes [1-(Ph 2 P)-η 5 -C 9 H 6 ] 2 Ln III N(SiMe 3 ) 2 , Ln = La (1-La), Sm (1-Sm), were prepared by heating two equivalents of 1-(Ph 2 P)C 9 H 7 with Ln III [N(SiMe 3 ) 2 ] 3 in toluene at 100 °C. The treatment of 1-La with one equivalent of benzonitrile gave (PhCN)[1-(Ph 2 P)-η 5 -C 9 H 6 ] 2 La III N(SiMe 3 ) 2 , 2, while no adduct was formed in case of the samarium derivative 1-Sm. The reaction of 1-La and 1-Sm with two equivalents of benzyl azide yielded the (phosphazido)indenyl complexes {1-[BnN 3 -κ N (Ph 2 )P]-η 5 -C 9 H 6 }{1-[BnN 3 -κ 2 N , N '(Ph 2 )P]C 9 H 6 }Ln III N(SiMe 3 ) 2 , Ln = La (3-La), Sm (3-Sm), respectively. The five complexes catalyse the intramolecular hydroamination/cyclisation of 2,2-diphenylpent-4-ene-1-amine using 2% catalyst loading. All compounds were characterised by NMR and UV-Vis spectroscopy, single-crystal X-ray diffraction, and elemental analysis and DFT calculations were performed for 3-La.