Zirconium complexes involving 2-phosphorus-substituted indenyl fragments

A series of 2-R2P-substituted indenes, where R2P = Ph2P, Cy2P, (Pr2P)-Pr-i, and Bu-t(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, Bu-t(Cl)P, and (Bu2P)-Bu-t substituents at position 2 were obtained through the reaction of 1H-inden-2-ylphosphonous dichloride with MeLi, (BuMgCl)-Bu-t, and (BuMgCl)-Bu-t/(BuLi)-Bu-t-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 (BuPH2)-Bu-t with 2 equiv of 2-bromo-1H-indene. Triethylamine-promoted condensation of indenes bearing P(H)tBu and P(Cl)tBu fragments gave a mixture of cis- and trans-bis-indenyldiphosphines. Zirconium complexes (2-R2P-indenyl)(2)ZrCl2 (R2P = Ph2P, Me2P, Cy2P, (Pr2P)-Pr-i, (Bu2P)-Bu-t), as well as ansa-zirconocenes RP(2-indenyl)(2)ZrCl2 (R = Ph, Bu-t), were obtained in good yields from ZrCl4(THF)(2) and lithium salts of the respective 2-P-substituted indenes. Ansa-zirconocene ((BUP)-B-t)(2)(2-indenyl)(2)ZrCl2 including a P2R2 bridge was synthesized in a similar manner and isolated as the pure rac-isomer.