Zirconium complexes involving 2-phosphorus-substituted indenyl fragments

A series of 2-R2P-substituted indenes, where R2P = Ph2P, Cy2P, iPr2P, and tBu(H)P, were obtained via Pd-catalyzed reactions of 2-bromo-1H-indene (or 1H-inden-2-yl trifluoromethane sulfonate) with R2PH/Et3N. Analogous indenes bearing Me2P, tBu(Cl)P, and tBu2P substituents at position 2 were obtained through the reaction of 1H-inden-2-ylphosphonous dichloride with MeLi, tBuMgCl, and tBuMgCl/tBuLi−CuCN, respectively. Diethyl 1H-inden-2-ylphosphonate, prepared via the Ni-catalyzed Arbuzov reaction of 2-bromo-1H-indene with P(OEt)3, was found to be a convenient starting material for the synthesis of 2-H2P-substituted indene. 1H-Inden-2-yl(phenyl)phosphine, prepared via the Pd-catalyzed arylation of 2-H2P-substituted indene by PhI, turned out to react with 2-bromo-1H-indene in the presence of Pd(PPh3)4 and Et3N to form di(1H-inden-2-yl)(phenyl)phosphine in almost quantitative yield. Analogously, di(1H-inden-2-yl)(tert-butyl)phosphine was prepared via catalytic reaction of tBuPH2 with 2 equiv of 2-bromo-1H-inden...