Palladium-arene interactions in catalytic intermediates: an experimental and theoretical investigation of the soft rearrangement between eta1 and eta2 coordination modes

A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl]2*CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C(ipso) atom of the arene lies almost at the fourth planar coordination site of the metal [Pd-C(ipso) = 2.22(1) A (average)], and due to the arene's tilting, the substituted C(ortho) atom is relatively close to the metal atom [2.54(1) A (average)]. The coordinated C(ipso)-C(ortho) linkage, in a seemingly dihapto coordination, is anti with respect to the CH2 bridge of the bicycloheptyl unit. Variable-temperature NMR experiments for the para-substituted dimer 9 reveal restricted rotation of the two aryl groups about the corresponding C-C(ipso) bonds (DeltaE < or =17 kcal x mol(-1)). DFT-B3LYP calculations have been carried out on the known and similar monomer (phenylbicycloheptenyl)Pd(PPh3)I (4) and its related substituted derivatives. The essential results are as follows: (i) The potential energy surface for twisting the phenyl ring away from the symmetric eta(1) coordination in 4 is very flat (DeltaE < or = 1 kcal x mol(-1)) whereas an Atoms in Molecules analysis excludes the existence of an actual Pd-C(ortho) bond in the seemingly eta2-type conformer. (ii) Complete rotation of the unsubstituted phenyl ring is not facile but feasible. A significant strain affects the transition-state structure featuring a Pd-HC(aryl) agostic-type bond. The calculated destabilization of 10.3 kcal x mol(-1), with respect to the ground state, can be compared to the experimental barrier of the dimer 9. (iii) Various methyl-substituted derivatives of 4 have been optimized, and their structural and energetic trends are discussed. An almost ideal eta1 coordination is shown by the anti conformer of the C(ortho)-substituted complex due steric effects. For all of the other cases, a slipped eta2 coordination may be described. As a general conclusion, the unsaturated metal center receives pi electron density of the arene mainly through its C(ipso) atom. The effect may be slightly improved if the C(ortho) atom also gets closer to the metal, but in no case, does the slipped eta2 coordination seem to be crucial for the stability of the system.     

Cation-controlled self-assembly of a hexameric europium wheel

The simple asymmetric tetradentate ligand 2,2':6',2' '-terpyridine-6-carboxylic acid leads to the self-assembly of the first europium nanowheel containing europium ions in two different coordination environments. Moreover the self-assembly of bis(terpyridinecarboxylate) europium species to form a hexameric wheel capable of strongly binding LnIII cations is controlled by the ligand/cation ratio.     

A new class of C1-symmetric monosulfoximine ligands for enantioselective hetero Diels-Alder reactions

Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee.     

New polythiophenes bearing electron-acceptor phthalocyanine chromophores

Two new donor-acceptor copolymers comprising a polythiophene backbone, and bearing phthalocyanine chromophores on the side chains have been prepared. Preliminary photophysical characterization of these materials by FTIR photoinduced absorption indicates that electron transfer from the polythiophene to the phthalocyanine units takes place.     

One-pot palladium-catalyzed synthesis of 2,3-disubstituted bicyclo[2.2.1]heptanes and bicyclo[2.2.1]hept-5-enes

A new and highly stereoselective palladium-catalyzed synthesis is reported, based on two subsequent insertions of the bicyclo[2.2.1]heptene system into an aryl or vinylpalladium bond, formed in situ from aryl or vinyl bromides.     

A modular nanoparticle-based system for reagentless small molecule biosensing

Metalloprotein tethered CdSe nanoparticles have been generated to provide selective and reagentless maltose biosensing. As opposed to cell or protein detection by semiconducting nanoparticle bioconjugates, a modular method for small-molecule detection using semiconducting nanoparticle bioconjugates has been difficult. Here we report a method for reagentless protein-based semiconducting nanoparticle biosensors. This method uses Ru(II) complex-CdSe nanoparticle interactions and the maltose-induced conformation changes of maltose binding protein to alter the CdSe nanoparticle fluorescence emission intensity. In this proof-of-principle system, the maltose-induced protein conformation changes alter the Ru(II) complex-CdSe nanoparticle interaction, which increases the CdSe emission intensity. Altered CdSe emission intensity effects are best described as electron transfer from the Ru(II) complex to the CdSe excited state forming the nonfluorescent CdSe anion. Four surface-cysteine, Ru(II) complex-attached maltose-binding proteins have been studied for maltose dependent alteration of CdSe emission intensities. With 3.0-3.5 nm diameter CdSe nanoparticles, all ruthenated maltose-binding proteins display similar maltose-dependent increases (1.4-fold) in CdSe emission intensity and maltose binding affinities (KA = 3 x 106 M-1). For these four systems, the only difference was the sample-to-sample variation in maltose-dependent responses. Thus, very few surface cysteine mutations need to be examined to find a successful biosensor, as opposed to analogous systems using organic fluorophores. This strategy generates a unimolecular, or reagentless, semiconducting nanoparticle biosensor for maltose, which could be applied to other proteins with ligand-dependent conformation changes.     

The effect of pyridinecarboxylate chelating groups on the stability and electronic relaxation of gadolinium complexes

The ligand N,N'-bis[(6-carboxy-2-pyridylmethyl]ethylenediamine-N,N'-diacetic acid (H(4)bpeda) was synthesised using an improved procedure which requires a reduced number of steps and leads to a higher yield with respect to the published procedure. It was obtained in three steps from diethylpyridine-2,6-dicarboxylate and commercially available ethylenediamine-N,N[prime or minute]-diacetic acid with a total yield of approximately 20%. The crystal structure of the hexa-protonated form of the ligand which was determined by X-ray diffraction shows that the four carboxylates and the two amines are protonated. The crystal structure of the polynuclear complex [Gd(bpeda)(H(2)O)(2)](3)[Gd(H(2)O)(6)](2)Cl(3)(2), isolated by slow evaporation of a 1:1 mixture of GdCl(3) and H(4)bpeda at pH approximately 1, was determined by X-ray diffraction. In complex three [Gd(bpeda)(H(2)O)(2)] units, containing a Gd(III) ion ten-coordinated by the octadentate bpeda and two water molecules, are connected in a pentametallic structure by two hexa-aquo Gd(3+) cations through four carboxylato bridges. The protonation constants (pK(a1)= 2.9(1), pK(a2)= 3.5(1), pK(a3)= 5.2(2), and pK(a4)= 8.5(1)) and the stability constants of the complexes formed between Gd(III) and Ca(II) ions and H(4)bpeda (log beta(GdL)= 15.1(3); log beta(CaL)= 9.4(1)) were determined by potentiometric titration. The unexpected decrease in the stability of the gadolinium complex and of the calcium complex of the octadentate ligand bpeda(4-) with respect to the hexadentate ligand edta(4-) has been interpreted in terms of an overall lower contribution to stability of the metal-nitrogen interactions. The EPR spectra display very broad lines (apparent DeltaH(pp) approximately 800-1200 G at X-band and 90-110 G at Q-band depending on the temperature), indicating a rapid transverse electron spin relaxation. At X-band, Gd(bpeda) is among the fastest relaxing Gd(3+) complexes to date suggesting that the presence of pyridinecarboxylate chelating groups in itself does not lead to slow electron relaxation.     

A new catalytic method for the synthesis of selectively substituted biphenyls containing an oxoalkyl chain

A novel reaction sequence leading to the synthesis of substituted biphenyls containing a carbonyl group in an aliphatic chain has been achieved in one-pot reaction starting from iodoarenes and allylic alcohols under the catalytic action of palladium and norbornene. The latter is temporarily incorporated into a palladacycle, which directs the reaction towards the selective formation of an arylaryl bond. Norbornene spontaneously deinserts to allow the biphenylylpalladium bond thus formed to react in its turn with the allylic alcohol.