Chapter05.June02 - Chapter 5 Rates and Mechanisms of...

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26 Chapter 5 Rates and Mechanisms of Reactions of Coordination Compounds The sections and subsections in this chapter are listed below. 5.1 A Brief Survey of Reaction Types 5.2 Labile and Inert Coordination Compounds 5.3 Substitution Reactions of Octahedral Complexes Possible Mechanisms Experimental Complications Evidence for Dissociative Mechanisms Explanation of Inert versus Labile Complexes 5.4 Redox or Electron Transfer Reactions Outer-Sphere Mechanisms Inner-Sphere Mechanisms 5.5 Substitution Reactions in Square Planar Complexes: The Kinetic Trans Effect
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27 Chapter 5 Objectives You should be able to recognize the various types of reactions that coordination compounds undergo substitution (including hydrolysis and anation), dissociation, addition, electron transfer (including oxidative-addition and reductive-elimination), reactions of coordinated ligands write expressions for overall and stepwise equilibrium constants for a given substitution reaction distinguish between and correctly use the kinetic terms labile and inert as well as the thermodynamic terms stable and unstable write dissociative (D), associative (A), and interchange (I) mechanisms for substitution reactions explain, when determining the rate law of a given reaction, how the concentration of a reactant may be masked by certain experimental conditions cite evidence from rates of exchange of water molecules as well as anation and aquation reactions, that substitution reactions of octahedral complexes most often follow a dissociative mechanism discuss the contributions of metal size and charge, steric hindrance among ligands, overall charge on the complex, and M-L covalent overlap to the energy of activation of the bond- breaking, rate-determining step of a substitution reaction discuss the contribution of the change of crystal field stabilization energy to the energy of activation of the bond-breaking, rate-determining step of a substitution reaction summarize why complexes of the first row transition metal ions, with the exception of Cr 3+ and Co 3+ , are generally labile while those of most second and third row transition metal ions are inert. describe outer-sphere electron transfer mechanisms and how their rates are a function of the relative M-L distances in the reactants describe inner-sphere electron transfer mechanisms and how their rates are a function of the polarizability of the bridging ligand describe the kinetic trans effect and rationalize it in terms of the polarizability of the trans- directing ligand be able to use the kinetic trans effect to outline the synthesis of various square planar complexes
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28 Solutions to Odd-Numbered Problems 5.1. K 1 K 2 K 3 K 4 = [{Cu(NH 3 )(H 2 O) 3 } 2+ ] x _ [{Cu(NH 3 ) 2 (H 2 O) 2 } 2+ ]__ x [{Cu(H 2 O) 4 } 2+ ][NH 3 ] [{Cu(NH 3 )(H 2 O) 3 } 2+ ][NH 3 ] ___ [{Cu(NH 3 ) 3 (H 2 O)} 2+ ]__ x _____[{Cu(NH 3 ) 4 } 2+ ] ____ [{Cu(NH 3 ) 2 (H 2 O) 2 } 2+ ][NH 3 ] [{Cu(NH 3 ) 3 (H 2 O)}
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This note was uploaded on 04/06/2010 for the course CHEMISTRY CHM 3610 taught by Professor Dr.kavallieratos during the Spring '10 term at FIU.

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Chapter05.June02 - Chapter 5 Rates and Mechanisms of...

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