Aspects of Organo-Transition-Metal

Aspects of Organo-Transition-Metal Photochemistry and Their Biological Implications... 

Reports of conferences organized by the New York Academy of Sciences are published in the Annals, and several of these contain either original contributions or review articles concerned with aspects of organo-transition metal chemistry. 

Prerequisite to any catalytic activity is the ability of the metal center to interact effectively with alcohols or alcohol-derived precursors. There are several ways in which this can occur, and most of these have been observed or postulated in at least one catalytic scheme. In order to understand the specific reactivities, though, the reader should be familiar with some fundamental aspects of organo-transition-metal chemistry. These will be discussed only very briefly. The reader should also recognize that in order for catalysis to occur, a balance of reactivities is required. 

Koerner von Gustorf, E. A. Leenders, L. H. G. Fischler, I. Perutz, R. N. "Aspects of Organo-transition Metal Photochemistry and their Biological Implications," Adv. Inorg. Chem. Radiochem., 1976, 19, 65. 

Redistribution Equilibria of Organometallic Compounds, 6, 171 Radiochemistry of Organometallic Compounds, 11, 207 Strengths of Metal-to-Carbon Bonds, 2, 49 Structural Aspects of Organotin Chemistry, 5, 137 Structural Chemistry of Organo-Transition Metal Complexes, 3, Structures of Organolithium Compounds, 3, 365 Transition Metal-Carborane Complexes, 8, 87 Transition Metal-Isocyanide Complexes, 11, 21... 

Organo-Transition Metal Compounds and Related Aspects of Homogeneous Catalysis , B. L. Shaw and N. I. Tucker, Chapter 53, Comprehensive Inorganic Chemistry, Pergamon Press, 1973. 

As mentioned above, although some examples of intramolecular MBH reactions have been reported in the literature, this aspect is still in its infancy. Most known reports are based on the cyclizations of combinations of enone-enone, enone-acrylate, enone-aldehyde, unsaturated thioester-aldehyde, enone-allylic carbonate frameworks, etc. More recently, Krafft et al. have developed a novel, entirely organo-mediated intramolecular MBH reaction by using allyl chloride 277 as an alternative electrophile to afford densely functionalized cyclic enones 278. This reaction tolerates modification of the enone and the use of primary and secondary allylic chlorides and generates both five-and six-membered rings in excellent yields. Both mono- and disubstituted alkenes are formed with excellent selectivity in the absence of a transition metal catalyst (Scheme 1.100). ... 

The stabilization of these heteroaldehydes and -ketones by coordination to transition metals is the subject of this review. Many problems connected with the high reactivity of these heterocarbonyl compounds can be circumvented by using their transition metal complexes. The chemistry of organo-sulfur and organoselenium transition metal complexes in more general terms30,31 and some aspects of thio- and selenoaldehydes and -ketones as... 

Abstract In this review, novel hierarchical self-assembled structures based on reversible organo-metaUic supramolecular polymers are discussed. Firstly, we discuss recent advances in the field of coordination polymers, considering cases in which transition metal ions and bis- or multiligands are used to build up organo-metallic supramolecular polymers. Secondly, we review hierarchical self-assembled structures based on these coordination polymers, such as polyelectrolyte layer-by-layer films, capsules, complex coacervate core micelles and microemulsions, and nanoribbons. Finally, we give a short perspective on the formation of coordinationpolymeric hierarchical self-assembled structures. The implications of fundamental and applied research, as well as aspects of new technologies are also discussed. 

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