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The synthesis of enantiomerically pure palladatricyclo[4.1.0.0(2,4)]heptanes and their modification by an unprecedented and very efficient positional selective transesterification is described. The mild reaction conditions are most probably based on an acceleration of the transesterification due to assistance by the metal. This novel approach allows straightforward access to a large number of structurally diverse organometallic complexes. The functional groups on the newly installed ester moieties were modified by using standard peptide synthesis protocols, Sonogashira reactions, and nucleophilic substitution reactions. The cellular uptake of these organometallic species was traced by confocal microscopy and their biological activity was evaluated by using different cell lines. Inhibition of cell growth and induction of apoptotic cell death by these novel palladium heterocycles are equivalent to Cisplatin.

The substrate scope, the mechanistic aspects of the gold-catalyzed oxazole synthesis, and substrates with different aliphatic, aromatic, and functional groups in the side chain were investigated. Even molecules with several propargyl amide groups could easily be converted, delivering di- and trioxazoles with interesting optical properties. Furthermore, the scope of the gold(I)-catalyzed alkylidene synthesis was investigated. Further functionalizations of these isolable intermediates of the oxazole synthesis were developed and chelate ligands can be obtained. The use of Barluenga's reagent offers a new and mild access to the synthetically valuable iodoalkylideneoxazoles from propargylic amides, this reagent being superior to other sources of halogens.

Starting from a silicon dichloro substituted silole and a silacyclobutene, a series of new organosilicon-based spiro compounds was synthesized by using standard organometallic reaction procedures. The spiro compounds that combine two organic photoactive subunits at one silicon center were fully characterized by the usual analytical and spectroscopic methods, which include molecular structure determination by single-crystal X-ray analysis. Photoluminescence spectra of the compounds were recorded in the solid state and also as dilute solutions in THF. Interpretation of the spectra revealed that photoluminescence in this series of compounds originated from the stilbene or its vinylogue subunits. Different linkages of these groups to the silicon atoms (cyclic or open structures, four- or five-membered cycles) strongly affected both the excitation and the emission spectra, which show different emission maxima depending on the state of the sample (solid state or in solution) and the wavelength of light used for excitation. Thus, owing to their optoelectronic properties these compounds might be useful tools for the design of sensitive sensor materials and of optical switches.

The effect of different substituents, such as bromo, chloromethyl, hydroxymethyl, formyl, acetyl, carboxy, and acylated hydroxymethyl and ammonium groups, on the furan ring of substrates in gold-catalyzed phenol synthesis has been investigated. The furan ring was also replaced by different heterocycles, such as pyrroles, thiophenes, oxazoles, and a 2,4-dimethoxyphenyl group; gold catalysis then delivered no phenols, but occasionally other products were obtained. [Ru(3)(CO)(12)] also catalyzed the conversion of 1 at a low rate, [Os(3)(CO)(12)] failed as a catalyst, and with [Co(2)(CO)(8)] the alkyne complex 19 can be obtained, it does not lead to any phenol but reacts with norbornene to give the product of a Pauson-Khand reaction. Efforts to prepare vinylidene complexes of 1 provided the only evidence for these species; in the presence of a phosphane ligand with ruthenium an interesting deoxygenation to 22 was observed. The phenol 2 c was converted to the allyl ether, a building block for para-Claisen rearrangements, and to the aryl triflate, a building block for cross-coupling reactions.

A comparison of the molecular structures of mono-, di- and tetraborylated ferrocenes [Fc{B(R(1))(R(2))}] (R(1)/R(2)=Br/Br, Br/Fc, Br/Me, Me/Me, Me/OH, OMe/OMe), 1,1'-[fc{B(R(1))(R(2))}(2)] (R(1)/R(2)=Br/Br, Br/Me, OMe/OMe), and 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)] revealed the boryl substituent(s) to be bent out of the Cp ring plane towards the iron center. The corresponding dip angle alpha* decreases with decreasing Lewis acidity of the boron atom and with increasing degree of borylation at the ferrocene core. This trend is well reproduced by DFT calculations (including [FcBH(2)], not yet accessible experimentally). A Bader analysis of the electron density topology of [FcBH(2)] (alpha*=26.5 degrees ; BP86/TZVP) clearly showed that there is no direct iron-boron bonding in this compound. Instead, strongly delocalized orbital interactions have been identified that involve the boron p orbital, C(ipso) of the adjacent Cp ring, d orbitals at iron, and a through-space interaction with the second Cp ring. A second important factor is attractive electrostatic interactions, which are enhanced upon ligand bending. Cyclic voltammetric measurements on the series [FcBMe(2)], 1,1'-[fc(BMe(2))(2)], and 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)] indicate a substantial anodic shift in the oxidation potential of the central iron atom upon introduction of BMe(2) substituents. Addition of 4-dimethylaminopyridine (DMAP) does not just counterbalance this effect, but leads to a cathodic shift of the Fe(II)/Fe(III) redox transition far beyond the half-wave potential of parent ferrocene. In the Mossbauer spectra, a continuous decrease in the quadrupole splitting (QS) is observed upon going from parent ferrocene to [FcBMe(2)], to 1,1'-[fc(BMe(2))(2)], and to 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)]. In contrast, no significant differences are found between the QS values of ferrocene, [Fc(BMe(2)-DMAP)], and 1,1'-[fc(BMe(2)-DMAP)(2)].

A modular approach to a new class of structurally diverse bidentate P/N, P/P, P/S, and P/Se chelate ligands has been developed. Starting from hydroquinone, various ligands were synthesized in a divergent manner via orthogonally bis-protected bromohydroquinones as the central building block. The first donor functionality (L1) is introduced to the aromatic (hydroquinone) ligand backbone either by Pd-catalyzed cross-coupling (Suzuki coupling) with hetero-aryl bromides, by Pd-catalyzed amination, or by lithiation and subsequent treatment with electrophiles (e.g., chlorophosphanes, disulfides, diselenides, or carbamoyl chlorides). After selective deprotection, the second ligand tooth (L2) is attached by reaction of the phenolic OH functionality with a chlorophosphane, a chlorophosphite, or a related reagent. Some of the resulting chelate ligands were converted into the respective PdX2 complexes (X = Cl, I), two of which were characterized by X-ray crystallography. The methodology developed opens an access to a broad variety of new chiral and achiral transition metal complexes and is generally suited for the solid-phase synthesis of combinatorial libraries, as will be reported separately.

Considerable configurational stability even for the radical, which should allow radical transformations with retention of configuration, is one of the most striking results obtained in a theoretical investigation into the structure and energetics of reactive intermediates in the chemistry of arene–Cr(CO)3 complexes (see picture), such as the benzylic anions, cations, and radicals, by using density functional methods.

The usefulness of the chiral transition metal π complex 1 as synthetic building block was demonstrated by its conversion into the functionalized enone 2, which in turn could be efficiently transformed into the marine natural product (+)-ptilocaulin (3). The crystal structures of 3 and rac-3 exhibit highly interesting patterns of hydrogen bonding resulting in helical or ribbonlike arrangements of the guanidinium nitrate monomers.