New Routes to η¹- and (η³↔η⁵)-Indenylpalladium Complexes: Synthesis, Characterization, and Reactivities

Abstract

The dimer {(η3-Ind)Pd(μ-Cl)}2 (6) reacts with t-BuNC to give the dimeric species {(η1-Ind)(t-BuNC)Pd(μ-Cl)}2 (10), whereas reaction with PR3 gives the complexes (η-Ind)Pd(PR3)Cl (R = Ph (4), Cy (7), Me (8), OMe (9)). Complexes 4 and (1-Me-Ind)Pd(PPh3)Cl (5) can also be prepared by reacting (PhCN)2PdCl2 with LiInd and PPh3. The structural characterization of complexes 4−7, 9, and 10 by 1H and 13C NMR spectroscopy and single-crystal X-ray diffraction studies has allowed an analysis of the indenyl ligand's mode of coordination, both in the solid-state and in solution. Compounds 4, 6, and 7 react with PhSiH3 in the absence of cocatalysts, whereas reaction with ethylene requires the presence of excess MAO to give polyethylene.

Interactions of Cationic Palladium(II)‐ and Platinum(II)‐η3‐Allyl Complexes with Fluoride: Is Asymmetric Allylic Fluorination a Viable Reaction?

“…Indenylpalladium( II ) Chloride (7c): In our hands, only the method reported by Lin and Boudjouk gave a pure product 42. Others have made similar observations 42b. We note that the use of 94 % EtOH in the synthesis is important because residual water favors the reaction.…”

Cationic palladium(ii)-indenyl complexes bearing phosphines as ancillary ligands: synthesis, and study of indenyl amination and anticancer activity

“…3 ), 110.0 (bt, C 2 ), 118.6 (CH, C 4 , C 7 ), 127.3 (CH, C 5 , C 6 ), 128.6 (C, t, J C-P = 3.1 Hz, C 3a , C 7a ) 31. P{ 1 H} NMR (162.0 MHz, CDCl 3 , T=298 K, ppm) δ: 57.7.…”

A Combined Experimental/Computational Study of the Mechanism of a Palladium‐Catalyzed Bora‐Negishi Reaction

“…Borylzinc reagent 1 6 and palladium complexes 9 a , 7 , 8 , 14 a and 17 were synthesized according to literature procedures. Other palladium precursors and organic substrates were obtained from commercial sources and used as received.…”