s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck%20reactie%20Beletskaya%20%20Chem.%20Rev.%20003009.pdf

The heck reaction as a sharpening stone of palladium catalysis.

The last 15 years of hydroformylation and carbonylation chemistry are reviewed, including technical and commercial aspects.

Progress in hydroformylation and carbonylation

The design of artificial catalysts able to compete with the catalytic proficiency of enzymes is an intense subject of research. Non-covalent interactions are thought to be involved in several properties of enzymatic catalysis, notably (i) the confinement of the substrates and the active site within a catalytic pocket, (ii) the creation of a hydrophobic pocket in water, (iii) self-replication properties and (iv) allosteric properties. The origins of the enhanced rates and high catalytic selectivities associated with these properties are still a matter of debate. Stabilisation of the transition state and favourable conformations of the active site and the product(s) are probably part of the answer. We present here artificial catalysts and biomacromolecule hybrid catalysts which constitute good models towards the development of truly competitive artificial enzymes.

/pdf/supramolecular-catalysis-part-2-artificial-enzyme-mimics-2h1esy0td8.pdf

Supramolecular catalysis. Part 2: artificial enzyme mimics

Metal alkynyl complexes hold a fascination for synthetic chemists, structural chemists, and materials scientists alike. Harnessing the unique overlap of metal and carbon orbitals is a challenge that can be overcome in many ways and hence, there are many synthetic routes toward M-C=C-bond-forming reactions that utilize a wide variety of transition-metal and alkynyl reagents. Some methods can be widely applied, while others are specific to a particular metal or compound. The linear geometry of the alkynyl unit and its pi-unsaturated character have led to metal alkynyls becoming attractive building blocks for molecular wires and polymeric organometallic materials, which can possess interesting properties, such as optical nonlinearity, luminescence, liquid crystallinity, and electrical conductivity. A unique, multifaceted approach, often combining talents from all three of the above chemical disciplines, has served as a driving force behind the intense research into the development of metal alkynyl sigma complexes, the progress of which, particularly in the last ten years, is summarized in this review.

Metal alkynyl σ complexes: Synthesis and materials

Organometallic molecular wires and other nanoscale-sized devices: An approach using the organoiron (dppe)Cp*Fe building block

Reaction of the butadiynyl complex ( 5 -C5Me5)Re(NO)(PPh3)(CtCCtCH) (ReC4H) with Cu- (OAc)2 (pyridine, 80 °C) gives the I-octatetraynediyl complex ReC8Re (70%). Analogous cross-coupling of ReC4H and ReC2H gives (after chromatography) ReC4Re (14%), ReC6Re (44%), and ReC8Re (15%). Longer sp carbon chains are accessed by reactions of ReC4H with n-BuLi and CuI, which give ReC4Cu. This isolable species is treated in situ with BrCtCSiEt3 or BrCtCCtCSiMe3 (excess EtNH2, THF) to give ReC6SiEt3 or ReC8SiMe3 (84-77%). Desilylations (wet n-Bu4N + F - ) yield ReC6H or ReC8H (88-73%). Then Cu(OAc)2 (pyridine, 50 °C) gives ReC12Re or ReC16Re (71-67%). The former is also available from ReC4Cu and BrCtCCtCBr (45%), and ReC10Re can be accessed by cross-coupling. ReC6H and ReC8H are similarly converted to ReC10SiR3 (R ) Me, Et; 51-26%) and ReC12SiMe3 (43%). Desilylation of ReC10SiR3 gives labile ReC10H, but only black powder is obtained from ReC12SiMe3. In situ coupling of ReC10H gives ReC20Re (52-34%), which unlike lower homologues is not obtained in analytically pure form. The effects of chain length upon visible spectra (progressively red-shifted and more intense bands; >190 000 M -1 cm -1 ), IR/ Raman OCtC patterns (progressively more bands), 13 C NMR chemical shifts (asymptotic limit of 64-67 ppm for ReCtC(CtC)n), cyclic voltammetry (decreased reversibility of two oxidations; a gradual shift of the first to thermodynamically less favorable potentials, so that only a single oxidation is observed for ReC20Re), and thermal stabilities (solid-state decompositions at 155 °C, ReC20Re, and 178-217 °C, lower homologues) are studied in detail.

Toward Metal-Capped One-Dimensional Carbon Allotropes: Wirelike C6-C20 Polyynediyl Chains That Span Two Redox-Active

A Step-Growth Approach to Metal-Capped One-Dimensional Carbon Allotropes: Syntheses of C12, C16, and C20 μ-Polyynediyl Complexes

One major objective has been the preparation of compounds in which sp carbon chains span two metals, L{sub n}M(C){sub x}M`L`{sub n`} (I). There are now many examples of such C{sub 2} complexes. However, higher homologs remain much less well explored. We have been particularly attracted by the potential for charge transfer phenomena involving the metal termini in I. Several strategies have been utilized to prepare complexes of the type I. However, we felt that the deprotonation of ethynyl complexes L{sub n}MC=CH, or higher homologs, should afford nucleophilic conjugate bases that would allow syntheses of previously inaccessible classes of adducts. Thus, reactions of chiral rhenium ethynyl complexes and their structures are described here. 45 refs., 4 figs., 3 tabs.

Synthesis, Structure, and Redox Chemistry of Heteropolymetallic Carbon Complexes with MC2M', MC4M', and MC4M'C4M Linkages. Transmetalations of Lithiocarbon Complexes (.eta.5-C5Me5)Re(NO)(PPh3)(C.tplbond.CLi) and (.eta.5-C5Me5)Re(NO)(PPh3)(C.tplbond.CC.tplbond.CLi)

Two-Phase Hydroformylation of Octene-1 with Rhodium Complexes of P[C6H4(CH2)mC6H4-p-SO3Na]3 (m = 3, 6). Rate and Selectivity Enhancement with Surface-Active Phosphines

Comments on the synthesis of trisulfonated triphenylphosphine: reaction monitoring by NMR spectroscopy

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