Abstract
The phosphinoindenyl rare-earth metal complexes [1-(Ph2P)-η5-C9H6]2LnIIIN(SiMe3)2, Ln = La (1-La), Sm (1-Sm), were prepared by heating two equivalents of 1-(Ph2P)C9H7 with LnIII[N(SiMe3)2]3 in toluene at 100 °C. The treatment of 1-La with one equivalent of benzonitrile gave (PhCN)[1-(Ph2P)-η5-C9H6]2LaIIIN(SiMe3)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-[BnN3-κN(Ph2)P]-η5-C9H6}{1-[BnN3-κ2N,N′(Ph2)P]C9H6}LnIIIN(SiMe3)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.
Highlights
Cyclopentadienyl ligands are among the work horses of organometallic rare-earth metal chemistry
In terms of diorganophosphorus-substituted indenyl complexes, examples of the rare earth complexes are limited to phosphazenes and phosphonium derivatives instead, in which the phosphorus is utilised to bind an additional donor to engage in chelation along with the indenyl group
We demonstrated the preparation of the indenyl lanthanum (1-La) and samarium (1-Sm) complexes by protonolysis reactions from 3-(diphenylphos-phino)indene and Ln[N(SiMe3)2]3 (Ln = La, Sm)
Summary
Cyclopentadienyl ligands are among the work horses of organometallic rare-earth metal chemistry. In terms of diorganophosphorus-substituted indenyl complexes, examples of the rare earth complexes are limited to phosphazenes and phosphonium derivatives instead, in which the phosphorus is utilised to bind an additional donor to engage in chelation along with the indenyl group. As part of these works, rare-earth metal phosphazenoindenyl complexes have been shown to be active hydroamination catalysts.[15]. We present the first examples of rare-earth phosphinoindenyl and phosphazidoindenyl complexes and our studies exploring their reactivity including their activity to catalyse intramolecular hydroamination reactions
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
