Palladium-catalyzed coupling reactions of 6,6'-dihydroxyboron-2,2'-dimethoxy- 1, 1'-binaphthyl 5g and chloroarenetricarbonylchromium complexes 6a - c afforded complexes 7a - c with the binaphthyl residue directly linked to the (eta(6)-arene)tricarbonylchromium entity. Coupling reactions of 2,2'-dimethoxy, 3,3'diodo, and 6,6'-diodo- 1, 1'-binaphthyl A and 5h with ethynylarenetricarbonylchromium derivatives 6d - f and ethynylferrocene 9 yielded binaphthyl compounds linked to arenetricarbonylchromium and ferrocenyl derivatives 8a - c, 11a - c, 10, and 12 through a triple bond. Condensation of 2,2'-dimethylmethoxy, 3-formyl, 1,1'-binaphthyl 2a with (eta(6)-phenyl)methyltriphenylphosphonium tricarbonylchromium 13 and ferrocenylmethyltriphenylphosphonium 18 gave binaphthyl compounds linked to arenetricarbonylchromium and ferrocenyl derivatives 14 and 19, respectively, through a double bond. X-ray analyses of the dinuclear chromium complex 8a and of the mononuclear chromium complex 17-Z are described.

In order to investigate the non-linear optical properties, in particular second-order effects of binuclear organometallic complexes, a series of new cationic binuclear [MCp-(DPPE)Nequivalent toC-(spacer)-Cequivalent toC-C6H5Cr(CO)(3)](+)[PF6](-) compounds and mononuclear precursors [Nequivalent toC-(spacer)-Cequivalent toC-C6H5Cr(CO)(3)] have been synthesised [where M = Fe-II or Ru-II; Cp = eta(5)-C5H5 and spacer = phenyl ring (C6H4), thiophene, (C4H2S), or bithiophene (C4H2S)(2)]. The Fe or Ru organometallic pi-donor fragments were linked by an extended pi system to the acceptor Cr(CO)(3) fragment. The effect of pi back-donation involving the second Fe or Ru metal centre and the pi(*) orbitals of the Nequivalent toC-coordinated group, was probed by the nu((Nequivalent toC)) stretching bands on the IR spectra and also by NMR spectroscopic data. The planarity, largely due to the pi-electron resonance, found on the solid state structure of the mononuclear complex [Nequivalent toC-C6H5-Cequivalent toC-(eta(6-)C(6)H(5))Cr(CO)(3)] (1Cr) determined by X-ray diffraction [monoclinic system, P2(1)/c space group, with a = 10.326(2) Angstrom, b = 13.209(5) Angstrom, c = 11.799(2) Angstrom and Z = 4] emphasises the electronic effect of this building block. The significant values of first hyperpolarisability beta determined by hyper-Rayleigh scattering (HRS) indicate that the Fe containing compounds were more efficient on second-order non-linear optical properties than the ruthenium analogues and the parent mononuclear chromium compounds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

The reaction of (chloroarene)tricarbonylchromium with hexaalkylditin under palladium catalysis does not proceed by the expected Stille reaction with addition of an SnR3 group but, instead, affords alkylarene complexes via a postulated chromium-assisted alkyl migration.

The synthesis of novel bimetallic organochromium/organoiron monocation dipoles comprising π-conjugated complexes linked with conjugated spacers has been performed utilising Stille and Sonogashira coupling reactions. This work establishes a general strategy for the synthesis of mixed-metal chromium/dipole complexes for evaluation for nonlinear optical effects by hyper-Rayleigh scattering.

The synthesis of nitrile ligands linked to tricarbonyl (η6-arene)chromium complexes by conjugated spacers is performed by reacting aromatic bromo nitrile derivatives with tricarbonylchromium-complexed phenylacetylene using Sonogashira coupling reaction.

Treatment of tricarbonyl(η6-1,2,3-trimethoxybenzene)chromium complex 1 with acetonitrile carbanion in THF and then with iodine followed by reduction of the nitrile function gives mescaline. Deprotonation of complex 1 at the C5 carbon with LiTMP followed by chlorination, bromation or iodation gives 5-chloro, 5-bromo or 5-iodo complexes, useful synthons in organic synthesis for the preparation of 1,2,3-trimethoxy-5-substituted derivatives, precursors of natural products.

Deprotonation of(h(6)-1,2,3-trimethoxybenzene) tricarbonyl chromium with n-BuLi occurs mainly at the C4 carbon while the use of LiTMP gives predominantly the C5-substituted product. (C) Academie des Sciences/Elsevier, Paris.