Advanced Applications of NMR to Organometallic Chemistry by Marcel Gielen, Rudolph Willem, Bernd Wrackmeyer

By Marcel Gielen, Rudolph Willem, Bernd Wrackmeyer

This new sequence deals major contributions via popular chemists reviewing the cutting-edge of this extensive examine zone. actual Organometallic Chemistry goals to boost new insights and to advertise novel curiosity and investigations appropriate to organometallic chemistry. NMR spectroscopy has had a substantial impression on many fields of chemistry, even though it has served organometallic chemistry quite often on a regimen point. In a suite of studies, major chemists supply an perception into the scope of functions and discover the opportunity of this system for organometallic chemists. complicated purposes of NMR to Organometallic Chemistry;* Illustrates how contemporary 1D and second and really expert multinuclear purposes can resolve particular difficulties encountered by way of organometallic chemists* Surveys smooth NMR thoughts in organometallic chemistry* comprises steel NMR comparable options* specializes in the appearance of reliable country NMR in organometallic chemistryThis e-book will end up worthwhile to the NMR spectroscopist and organometallic chemists and also will be of curiosity to all natural, inorganic and actual chemists Contents: Selective Excitation and Selective Detection in ?29Si NMR; Two-dimensional ?13C, steel Nuclei Correlation; Two-dimensional ?1H-?119Sn Proton Detected Correlation Spectroscopy in Coordination Chemistry of Hypervalent Organotin Compounds; oblique Nuclear ?119Sn-X Spin-Spin Coupling; reliable country NMR functions in Organotin and Organolead Chemistry; stable country NMR Investigations of steel Carbonyl Complexes; excessive strain NMR in Organometallic Chemistry; Multinuclear NMR Spectroscopy in Supercritical Fluids; excessive solution ?6,7Li NMR of Organolithium Compounds; steel NMR of Organovanadium, -Niobium and -Tantalum Compounds; NMR of steel Nuclei in Clusters; ?171Yb NMR Spectroscopy

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O 2 R C .. O .. : CarboxylatAnion Anode (Oxidation) − e0 − O 2 R C .. O .. CarboxyRadikal . Decarboxylierung − 2 CO2 2R . 7 Reaktionen Die "gesättigten" Alkane reagieren selbst bei höheren Temperaturen im Gegensatz zu den "ungesättigten" Alkenen und Alkinen nicht mit konzentrierten Mineralsäuren, Basen, Oxidations- oder Reduktionsmitteln. Die früher wegen ihrer gleichartigen Reaktivität als Paraffine (lat. par affinis = gleich benachbart) bezeichneten Alkane sind wenig reaktive, unpolare, inerte Verbindungen: Typische Alkan-Reaktionen wie die Oxidation und Halogenierung verlaufen bei hohen Temperaturen.

3 1500 °C + O2 + H 2O 850 °C, Ni-Katalyse 2H C C H 3 H2 + + 10 H 2 + 2 CO CO Autoxidation Verzweigte Alkane mit tertiären C-Atomen (R3CH) reagieren in Gegenwart von Schwermetallspuren, Bromwassertoff oder bei leicht erhöhter Temperatur mit Luftsauerstoff, der als Biradikal (Triplett-Sauerstoff) vorliegt und sich zwischen die CH-Bindung schiebt. Bei dieser Autoxidation entstehen hochreaktive, teils explosive Alkylhydroperoxide. CH3 H3C C H CH3 + O2 (Luf t) 140 °C CH 3 O H H 3C C O CH 3 t-Butylhydroperoxid n-Alkane neigen kaum zur Autoxidation.

CH2 CH3 H3C CH2 CH2 CH2 CH Die längste C-Kette hat acht C-Atome: Octan ist das Grundskelett H3C C Br CH2 CH3 Man beziffere die C-Atome so, daß die Substituenten kleinstmögliche Positionsziffern erhalten. 8 7 6 5 CH2 CH3 4 Das Kohlenstoff-Atom mit höchster Substituentenzahl ist C-3 (nicht C-6). H3C CH2 CH2 CH2 CH H3C 3C Br CH2 CH3 2 1 Man benenne die Substituenten und gebe ihre Position in der Kette durch die entsprechende Ziffer an. 8 7 6 5 CH2 CH3 4 H3C CH2 CH2 CH2 CH 3-Methyl- H3C 3C Br 3-Brom- 4-Ethyl- CH2 CH3 2 1 Man bezeichne die Verbindung so, daß die Substituenten in alphabetischer Folge erscheinen.

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