Novel ruthenium dihydrogen complexes and their application in catalysis

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1. Verfasser: Prechtl, Martin 1978- (VerfasserIn)
Format: Buch
Sprache:English
Veröffentlicht: Duisburg [u.a.] WiKu-Verl. 2007
Schriftenreihe:Wissenschaftliche Monographie der MPG und der RWTH Aachen
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adam_text 1. Introduction 1 1.1. Background and Motivation 1 1.2. State ofthe Art and Objectives 2 1.2.1. Ruthenium Dihydrogen Complexes 2 1.2.2. Characterisation of Nonclassical Hydride Complexes 6 1.2.3. Catalysis 9 1.2.3.1. CH-Activation and H/D-Exchange Reactions 9 1.2.3.2. Ruthenium Hydrides in Hydrogen Transfer Processes 11 2. Results and Discussion 15 2.1. The Ruthenium Dihydrogen Complex [Ru(dtbpmp)(H2)H2] 15 2.1.1. Synthesis 15 2.1.2. Characterisation 17 2.1.3 Reactivity 23 2.1.3.1. H2 / N2 Exchange 23 2.1.3.2. H / D Exchange 26 2.1.3.3. Treatment with carbon monoxide 31 2.1.3.4. Reaction with pinacolborane 34 2.1.3.5. Reaction with CO2 36 2.1.4. Other PNP pincer ligands for ruthenium hydride complexes 40 2.2. The Ruthenium Dihydrogen Complex [Ru(dtbpoet)(H2)H2] 42 2.2.1. Synthesis 42 2.2.2. Characterisation 43 2.2.3. Reactivity 49 2.3. Catalysis 50 2.3.1. Catalytic ///D-Exchange between Aromatic Hydfocarbons and Deuterated Solvents 50 2.3.1.1. D2O as Deuterium Source 50 2.3.1.2. C6D6as Deuterium Source 58 2.3.2. Catalytic Dehydrogenation of Alcohol and Tandem Reactions 67 2.3.2.1. Dehydrogenative Coupling of Primary Alcohols 67 2.3.2.2. Dehydrogenation of Secondary Alcohols 77 3. Summary 82 3.1. Ruthenium Dihydrogen Complexes 82 3.2. Catalysis g4 4 Experimental Section gg 4.1. General og 4.2. Analytic Methods g( 4.2.1. Nuclear Magnetic Resonance Spectroscopy (NMR) 86 4.2.2. Mrared Spectroscopy (1R) gg 4.2.3. Mass Spectrometry gg 42A X ^y gg 4.2.5. Microanalysis 88 4.2.6. Autoclaves for High-Pressure Experiments 89 4.2.6.1. Typ I (glass autoclave, 50 mL) 89 4.2.6.2. Typ II (autoclave, 36 mL) 89 4-3. Synthetic Procedures 90 43.1. Uterature Compounds 90 4-3.2. Chelating Diphosphine Nitrogen Ligands (PNP-pincer) 91 43.3. Ruthenium Dihydrogen Complexes 92 4.3.3.1. Preparation of[Ru( M,pmp)H2(H2)] 4 92 43.3.2. Preparation of the complex [D,HRu( M,pm/?)H2(H2)] [D,]-4 94 43.3.3. Reaction of [Ru(d,bpmp)H2(H2)} 4 with C6D6 to highly deuterated [D,]-4 95 43.3.4. Reaction of RU(d,bpmp)H2(H2) 4 with D2O in C6DI2 to |D6|-4 / 26 95 43.3.5. Reaction of lRu(dtbpmp)H2(H2) 4 with N2 to RU(d,bpmp)H2(N2)] 20 96 4.3.3.6. Reaction of [Ru(dtbpmp)H2(H2)} 4 with carbon monoxide and hydrogen gas to [Ru(dtbpmp)(CO)H] 28 97 43.3.7. Reaction of [Ru(dtbpmp)H2(H2)] 4 with pinacolborane 97 43.3.8. Solid State Structure: Reaction with CO2 99 43.3.9. Preparation of lRu(,dtbpoet)H2(H2)} 5 104 4.3.3.10. Reaction of [Ru(dtbpoet)H2(H2)] 5 with N2 to [Ru(d,bpoe,)H2(N2)] 52 106 4.33.11. Reaction of [Ru(A^o«)H2(H2)l 5 with D2 to |DxHRu(rf/^oe,)H2(H2)l[Dx]-5 106 4-3.4. Catalysis ]07 4.3.4.1 Catalytic tf/D-exchange with D2O as Deuterium Source 107 4.3.4.2. Catalytic tf/D-exchange with [D6]benze„e as Deuterium Source 113 43.4.3. CatalyticDehydrogenationofAlcohols 119 5 Figure Index 126 6 Scheme Index 129 7 Table Index 132 8 Abbreviation Index 133 9 Compound Name Index 135 10 Compound Structure Index 138 11 Literature 146
any_adam_object 1
author Prechtl, Martin 1978-
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physical XIII, 152 S. graph. Darst.
publishDate 2007
publishDateSearch 2007
publishDateSort 2007
publisher WiKu-Verl.
record_format marc
series2 Wissenschaftliche Monographie der MPG und der RWTH Aachen
spellingShingle Prechtl, Martin 1978-
Novel ruthenium dihydrogen complexes and their application in catalysis
Hydridokomplexe swd
Katalyse swd
Rutheniumkomplexe swd
subject_GND (DE-588)4113937-9
title Novel ruthenium dihydrogen complexes and their application in catalysis
title_auth Novel ruthenium dihydrogen complexes and their application in catalysis
title_exact_search Novel ruthenium dihydrogen complexes and their application in catalysis
title_full Novel ruthenium dihydrogen complexes and their application in catalysis vorgelegt von Martin H. G. Prechtl
title_fullStr Novel ruthenium dihydrogen complexes and their application in catalysis vorgelegt von Martin H. G. Prechtl
title_full_unstemmed Novel ruthenium dihydrogen complexes and their application in catalysis vorgelegt von Martin H. G. Prechtl
title_short Novel ruthenium dihydrogen complexes and their application in catalysis
title_sort novel ruthenium dihydrogen complexes and their application in catalysis
topic Hydridokomplexe swd
Katalyse swd
Rutheniumkomplexe swd
topic_facet Hydridokomplexe
Katalyse
Rutheniumkomplexe
Hochschulschrift
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