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.

Recent Developments in the Chemistry of Polyvalent Iodine Compounds

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

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

Reactions of (η5-C5Me5)Re(NO)(PPh3)(C⋮CLi) with W(CO)6, Fe(CO)5, or Mn(CO)3(η5-C5HnCl5-n), followed by Me3O+ BF4-, give the heterobimetallic C3OMe complexes (η5-C5Me5)Re(NO)(PPh3)(C⋮CC(OMe))M(CO)x(η5-C5HnCl5-n)y (M/x/y/n = 3, W/5/0/−; 4, Fe/4/0/−; 5, Mn/2/1/5; 6, Mn/2/1/4; 7, Mn/2/1/0). Spectroscopic and crystallographic (3) data indicate contributions by +ReCCC(OMe)−M- resonance forms. Reactions of 4−7 and BF3 gas give the title compounds [(η5-C5Me5)Re(NO)(PPh3)(CCC)M(CO)x(η5-C5HnCl5-n)y (M/x/y/n = 9, Mn/2/1/5; 10, Mn/2/1/4; 11, Mn/2/1/0; 12, Fe/4/0/−). Spectroscopic and crystallographic (9) data indicate dominant contributions by fully cumulated +ReCCCMn resonance forms. Reactions of (η5-C5Me5)Re(NO)(PPh3)(C⋮CC⋮CLi) with Mn(CO)3(η5-C5Cl5), Mn(CO)3(η5-C5Br5), or Fe(CO)5, followed by Me3O+ BF4-, give the C5OMe complexes (η5-C5Me5)Re(NO)(PPh3)(C⋮CC⋮CC(OMe))M(CO)x(η5-C5X5)y (M/x/y/X = 16, Mn/2/1/Cl; 19, Mn/2/1/Br; 20, Fe/4/0/−). However, Mn(CO)3(η5-C5H5) does not react. Reaction of 16 and BF3 gives the C5 c...

New Forms of Coordinated Carbon: Wirelike Cumulenic C3 and C5 sp Carbon Chains that Span Two Different Transition Metals and Mediate Charge Transfer

Towards One-Dimensional Carbon Wires Connecting Single Metal Centers: A Cumulenic C5 Chain that Mediates Charge Transfer between Rhenium and Manganese Termini†

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