Modern Organoaluminum Reagents: Preparation, Structure, by Janusz Lewiński, Andrew E. H. Wheatley (auth.), Simon

By Janusz Lewiński, Andrew E. H. Wheatley (auth.), Simon Woodward, Samuel Dagorne (eds.)

Janusz Lewiński and Andrew E. H. Wheatley: uncomplicated trivalent organoaluminum species: views on constitution, bonding and reactivity.- Stephan Schulz: Organoaluminum complexes with bonds to s-block, p-block, d-block, and f-block steel centers.- Samuel Dagorne and Christophe Fliedel: Low valent organoaluminium (+I, +II) species.- Rudolf Wehmschulte: Organoaluminum species in homogeneous polymerization catalysis.- Paul Knochel, Tobias Blümke, Klaus Groll and Yi-Hung Chen: education of Organoalanes for natural Synthesis.- Yuki Naganawa and Keiji Maruoka: Reactions brought on through Lewis Acidic Organoaluminum Species.- Usein M. Dzhemilev and Vladimir A. D'yakonov: Hydro-, Carbo- and Cycloalumination of Unsaturated Compounds.- Andreas Kolb and Paultheo von Zezschwitz: Organoaluminum Couplings to Carbonyls, Imines and Halides.- Oscar P� mies and Montserrat Diéguez: Conjugate Addition of Organoaluminum Species to Michael Acceptors and comparable Processes.

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H. Wheatley 40 reacted with one equiv. [Ph3C][B(C6F5)4] in aromatic solvents at 25 C by net b-H abstraction to give base-free [(iPr2-ATI)AlR][B(C6F5)4] salts (R > Me) and the corresponding olefin [242]. Note that the three-coordinate Al methyl cations supported by a chiral or an achiral bisoxazolinato bidentate ligand appeared thermally unstable and readily degraded to unknown species [243]. Cationic {HC(CMeNAr)2}AlR+ and [(iPr2-ATI)AlR]+ species readily coordinated Lewis bases to form robust 4-coordinate {HC(CMeNAr)2}Al(R)(L)+ adducts.

Wheatley and catalytic transformations and future studies in the area will advance both fundamental and applied directions. 11 The Oxygenation of Alkylaluminum Compounds The insertion of dioxygen into a metal-carbon bond constitutes one of the oldest reactions in organometallic chemistry. The common wisdom states that the oxygenation reactions of homoleptic organometallic complexes are uncontrollably fast due to their postulated radical chain-reaction mechanism. The exact reaction mechanism is yet to be unambiguously described and debate about the details of the process is ongoing [273–276].

O Me Al N Ar THF 40 Scheme 5 Synthesis and structural diversity in organoaluminum supported by dianionic aminophenolate ligands center and held together by two C–HÁÁÁO bonds formed by the imino hydrogens and aryloxyde oxygen atoms; this results in the formation of a hydrogen-bonded molecular chain. 5 A substantial role in the molecular organization of this system [145]. Hydrogen bonding and other types of non-covalent interactions may also be of importance in controlling processes that take place at metal sites as well as in the rapidly developing fields of crystal engineering and material chemistry.

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