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Reaction of the bis(2‐pyridylimino)isoindole derivatives (10‐Me)‐BPI (1a), (11‐Me)‐BPI (1b), (11‐Br)‐BPI (1c), (4‐Me)‐BPI (1d) and 4‐Me‐10‐tBuBPI (1e) with [PdCl2(PhCN)2] and triethylamine in benzene gave the square‐planar palladium(II) complexes [PdCl{(10‐Me)‐BPI}] (2a), [PdCl{(11‐Me)‐BPI}] (2b), [PdCl{(11‐Br)‐BPI}] (2c), [PdCl(4‐MeBPI)] (2d) and [PdCl(4‐Me‐10‐tBuBPI)] (2e), respectively. Extraction of the crude product 2b with aqueous sodium carbonate solution led to the formation of the dinuclear carbonato‐bridged complex [{(11‐Me‐BPI)Pd}2(μ‐CO3)] (3) which was characterized by an X‐ray structure analysis. Reaction of 11‐Br‐BPI (1c) with a large excess (6 equiv.) of the acetylenes Me3SiCCH, Ph3SiCCH and PhCCH under Sonogashira conditions gave the alkynylated derivatives 11‐(Me3SiCC)‐BPI (4a), 11‐(Ph3SiCC)‐BPI (4b) and 11‐(PhCC)‐BPI (4c), which were metallated with bis(benzonitrile)dichloropalladium(II) to yield the PdII complexes [PdCl{11‐(Me3SiCC)‐BPI}] (5a), [PdCl{11‐(Ph3SiCC)‐BPI}] (5b) and [PdCl{11‐(PhCC)‐BPI}] (5c), respectively. The activity of 2b in the catalytic hydrogenation of C=C double bonds was tested for the reaction with styrene, 1‐octene and cyclohexene. The stability of the palladium complex, the reproducibility of the reaction kinetics, the different behaviour towards the three olefins chosen as substrates, as well as the possibility of isolating the non‐decomposed catalyst after several catalytic runs, provides circumstantial evidence for molecular catalysis with the BPI‐palladium complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

The copper complexes [Cu(4-MeBPI)(OAc)] (4), [Cu(4-Me-10-tBuBPI)(OAc)] (5) and [Cu(BTI)(OAc)] (6) [BPI = 1,3-bis(2-pyridylimino)isoindole, BTI = 1,3-bis(2-thiazolylimino)isoindole] were prepared by reaction of the protio ligands with copper(II) acetate. Compounds 4 and 6 were characterized by X-ray diffraction, establishing distorted square-planar coordination geometries of the copper ions. Two monoclinic modifications of 6 (6a and 6b) were found, both crystallizing in the space group P2 1 /c, but possessing different cell parameters. In contrast to 6a, which is monomeric in the crystal, the second monoclinic modification 6b has a more complicated crystal structure, which is composed of both monomeric complex units such as those found in 6a and infinite chains

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Several novel substituted bis(2‐pyridylimino)isoindolato (BPI) cobalt(II) and iron(II) complexes [M(BPI)(OAc)(H2O)] (M = Co: 1 ‐ 6, Fe: 7) have been synthesized by reaction of bis(2‐pyridylimino)isoindole derivatives with the corresponding metal(II) acetates. Reaction of 1‐6 with 1.5 ‐ 2 molar equivalents of t‐BuOOH gave the corresponding alkylperoxocobalt(III) complexes [Co(BPI)(OAc)(OOtBu)] (10 ‐ 15). Using an aqueous solution of t‐BuOOH (70 %), cyclohexene was selectively catalytically oxidized to the dialkylperoxide cyclohex‐2‐ene‐1‐t‐butylperoxide.