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Thermochemical and Thermodynamic Properties of Organometallic Compounds

1-56700-124-6 (Print)

Thermochemical and Thermodynamic Properties of Organometallic Compounds

I. B. Rabinovich
University of Nizhniy Novgorod, Nizhniy Novgorod, Russia

V. P. Nistratov
University of Nizhniy Novgorod, Nizhniy Novgorod, Russia

V. I. Telnoy
University of Nizhniy Novgorod, Nizhniy Novgorod, Russia

M. S. Sheiman
University of Nizhniy Novgorod, Nizhniy Novgorod, Russia


This monograph consists of three parts. Part 1 consists of descriptions of the principles of chemical thermodynamics, and provides a short but complete manual on the theory of chemical thermodynamics. Part 2 is devoted to the thermochemical properties of organometallic compounds. The enthalpies of formation of organic compounds of transition and nontransition metals, as well as the average enthalpies of breaking the metal-organic ligand chemical bonds are evaluated and discussed. Part 3 deals with the thermodynamic properties of organometallic compounds.

181 pages, © 1999

Table of Contents:

1 Principles of Chemical Thermodynamics
1.1 Introduction. The First Law of Thermodynamics and Thermochemical Calculations
1.1.1 The Subject and Basic Concepts of Thermodynamics
1.1.2 The First Law of Thermodynamics. Thermochemical Calculations
1.1.3 Enthalpy of Chemical Reactions and Hess Law
1.1.4 Calculation of Enthalpy of Chemical Reactions Based on Enthalpies of Formation of Reactants
1.2 Theory of Heat Capacity. Temperature Dependence of Enthalpy of Chemical Reactions
1.2.1 Heat Capacity
1.2.2 Quantum Theory of Heat Capacity of Monoatomic Solids by Einstein
1.2.3 Theory of Heat Capacity of Monoatomic Solids by Debye
1.2.4 Heat Capacity of Gases
1.2.5 Temperature Dependence of the Enthalpy of Chemical Reactions
1.3 The Second Law of Thermodynamics
1.3.1 The Entropy of a System as the Function of its Thermodynamic Probability (Boltzmann Formula)
1.3.2 Clausius Equation
1.3.3 Criteria for Proceeding and Equilibrium of Chemical Processes
1.4 Characteristic Functions and Basic Equations of Thermodynamics
1.4.1 Basic equations for Closed Systems
1.4.2 Temperature
1.4.3 Maxwell Relations
1.4.4 Fundamental Equations for Open Systems
1.5 Calculation of Entropy. The Third Law of Thermodynamics
1.5.1 Calculation of Entropy
1.5.2 The Third Law of Thermodynamics
1.6 Thermodynamic Equations Describing the Equilibria of Chemical Processes
References (Part One)
2 Thermochemical Properties of Organometallic Compounds
2.1 Introduction
2.2 Enthalpies of Formation of Transition Metal Organic Compounds
2.2.1 Metal Carbonyls
2.2.2 Cyclopentadienyl Compounds
2.2.3 Bis-arene Compounds
2.2.4 Qrganometallic Compounds Containing E-Alkyl; E-O-Alkyl; E-N-Alkyl cr-Bonds
2.3 Enthalpies of Formation of Organic Compounds of Non-transition Elements
2.3.1 Non-transition Element-Organic Compounds of the I-st Group
2.3.2 Non-transition Element-Organic Compounds of the II-nd Group
2.3.3 The III-rd Group Non-transition Element-Organic Compounds
2.3.4 Element-Organic Compounds of the IV-th Group
2.3.5 Element-Organic Compounds of the V-th Group
2.3.6 Element-Organic Compounds of the VI-th Group
2.4 Average Enthalpies of the Breakage of Chemical Bonds Formed by Metals in Organic Compounds
References (Part Two)
3 Thermodynamic Properties of Organometallic Compounds
3.1 Introduction
3.2 Metal Carbonyls
3.2.1 Chromium Hexacarbonyl
3.2.2 Molybdenum Hexacarbonyl
3.2.3 Tungsten Hexacarbonyl
3.2.4 Manganese Carbonyls, Mn2(CO)io and Mn(CO)5
3.2.5 Dirhenium Decacarbonyl
3.2.6 Iron Carbonyls
3.2.7 Carbonyls of Ruthenium and Osmium
3.2.8 Dicobaltoctacarbonyl
3.2.9 Nickel Tetracarbonyl
3.3 Mixed Carbonyl Compounds
3.3.1 Benzenechromiumtricarbonyl
3.3.2 Thiophenchromiumtricarbonyl
3.3.3 Selenophen- and Tellurophen-chromiumtricarbonyls
3.3.4 Pyrrolmanganesetricarbonyl
3.3.5 Pentacarbonylmanganesehalogenides
3.3.6 Pentacarbonyltechnetiumhalogenides
3.3.7 Pentacarbonylrheniumhalogenides
3.3.8 Tricarbonylnitrosylcobalt
3.4 Cyclopentadienyl Compounds
3.4.1 Dicyclopentadienylmagnesium
3.4.2 Dicyclopentadienylvanadium
3.4.3 Dicyclopentadienylchromium
3.4.4 Dicyclopentadienylmanganese
3.4.5 Dicyclopentadienyliron
3.4.6 Dicyclopentadienylruthenium
3.4.7 Dicyclopentadienylcobalt
3.4.8 Dicyclopentadienylnickel
3.4.9 Tricyclopentadienylyttrium
3.5 Mixed Cyclopentadienyl Compounds
3.5.1 Dicyclopentadienyltitaniumbenzoate
3.5.2 Dicyclopentadienyltitaniumdiferrocenyl
3.5.3 Dicyclopentadienyltitaniumdichloride
3.5.4 Dicyclopentadienylzirconiumdichloride
3.5.5 Dicyclopentadienylhafmumdichloride
3.5.6 Tris-(cyclopentadienyl)disulphide
3.6 Bis-Arene-Metal Compounds
3.6.1 Ethylbenzene-o-diethylbenzene-vanadium
3.6.2 Bis-Benzene Compounds of Vanadium, Chromium, Molybdenum and Tungsten
3.6.3 Bis-benzene-ehromium
3.6.4 Bis-ethylbenzene-chromium, Bis-isopropylbenzene-chromium, Bis-arene-chromium-halogenides
3.7 Copper and Silver Acetylenides
3.8 Alkyl-Element Compounds
3.8.1 Dimethylzinc
3.8.2 Diethylzinc
3.8.3 Dimethylcadmium
3.8.4 Dimethylmercury
3.8.5 Diethylmercury
3.8.6 Trimethylaluminum
3.8.7 Triethylaluminum
3.8.8 Tripropylaluminum
3.8.9 Diisobutylaluminum
3.8.10 Trimethylgallium
3.8.11 Trimethylindium
3.8.12 Triethylindium
3.8.13 Tetramethylsilane
3.8.14 Tetraethylsilane
3.8.15 Tetramethylgermanium
3.8.16 Tetraethylgermanium
3.8.17 Tetra-n-butylgermanium
3.8.18 Tetramethyltin
3.8.19 Tetraethyltin
3.8.20 Tetra-n-pentyltin
3.8.21 Tetramethyllead
3.8.22 Tetraethyllead
3.8.23 Trimethylarsine
3.8.24 Triethylarsine
3.8.25 Triethylantimony
3.8.26 Triethylbismuth
3.8.27 Dimethylselenium
3.8.28 Dimethylselenium
3.8.29 Dipentyltellurium
References (Part Three)
Subject Index