Organometallic Chemistry
eBook - ePub

Organometallic Chemistry

Fundamentals and Applications

Ionel Haiduc

Share book
  1. 443 pages
  2. English
  3. ePUB (mobile friendly)
  4. Available on iOS & Android
eBook - ePub

Organometallic Chemistry

Fundamentals and Applications

Ionel Haiduc

Book details
Book preview
Table of contents
Citations

About This Book

This book provides the reader with a comprehensive introduction to the topic of organometallic chemistry. With an easy to follow structure covering both nontransition metals and transition metals as well as the applications of organometallic reagents in organic synthesis, this book is a must-have for the organometallic chemist.

Frequently asked questions

How do I cancel my subscription?
Simply head over to the account section in settings and click on ā€œCancel Subscriptionā€ - itā€™s as simple as that. After you cancel, your membership will stay active for the remainder of the time youā€™ve paid for. Learn more here.
Can/how do I download books?
At the moment all of our mobile-responsive ePub books are available to download via the app. Most of our PDFs are also available to download and we're working on making the final remaining ones downloadable now. Learn more here.
What is the difference between the pricing plans?
Both plans give you full access to the library and all of Perlegoā€™s features. The only differences are the price and subscription period: With the annual plan youā€™ll save around 30% compared to 12 months on the monthly plan.
What is Perlego?
We are an online textbook subscription service, where you can get access to an entire online library for less than the price of a single book per month. With over 1 million books across 1000+ topics, weā€™ve got you covered! Learn more here.
Do you support text-to-speech?
Look out for the read-aloud symbol on your next book to see if you can listen to it. The read-aloud tool reads text aloud for you, highlighting the text as it is being read. You can pause it, speed it up and slow it down. Learn more here.
Is Organometallic Chemistry an online PDF/ePUB?
Yes, you can access Organometallic Chemistry by Ionel Haiduc in PDF and/or ePUB format, as well as other popular books in Physical Sciences & Inorganic Chemistry. We have over one million books available in our catalogue for you to explore.

Information

Publisher
De Gruyter
Year
2022
ISBN
9783110695441

Part I: General

1 The scope of organometallic chemistry

Organometallic chemistry is the discipline dealing with compounds containing at least one direct metalā€“carbon bond. It should be added that organometallic chemistry deals with compounds in which an organic group is attached to an atom which is less electronegative than carbon (electronegativity X = 2.50). On this basis, the organic derivatives of some non-metals (with the electronegativities shown in brackets), namely boron (X = 2.01), silicon (X = 1.74) and arsenic (X = 2.20) are traditionally included in organometallic chemistry, although these elements are not metals (but often described as metalloids). In this volume, the organic derivatives of B, Si, Ge and As are not included, assuming that their metallic character is not predominant.
All elements, except the noble gases (other than xenon), form compounds with elementā€“carbon bonds. Therefore, organometallic chemistry embraces the organic derivatives of the alkali and alkaline earth metals, the non-transition metals (Main groups 13ā€“15), the transition metals (d-block elements, plus lanthanides and actinides) and some nonmetals (or metalloids) such as boron, silicon, antimony and tellurium.
It should also be mentioned that several classes of compounds which contain a metal and carbon in their composition, are not described as organometallic if a direct metalā€“carbon bond is absent. Thus, compounds such as metal alkoxides (with M_OR bonds), metal amides (with Mā€“N bonds), chelate complexes (e.g., acetylacetonates) or the metal salts of carboxylic acids, are not considered organometallic. Often, such compounds are described as metal organic.
Perhaps a classification as described may seem somewhat arbitrary but it is practical and generally accepted.

2 Organometallic molecules: the nature of metalā€“carbon bonds

The stability and reactivity of various organometallic compounds are very different. Some are very sensitive and react spontaneously with oxygen and water or are thermally unstable, whereas others are perfectly stable and can be handled in open atmosphere at room temperature without any special precautions. The chemical properties of organometallic compounds are determined by the nature of the metalā€“carbon bonds, and they can differ very much between various metals.
The classical bond types, covalent and ionic, are present in many organometallic compounds, but there are some metalā€“carbon interactions discovered and present only in the metalā€“carbon compounds.

2.1 Sigma-covalent (bicentric bielectronic) metalā€“carbon bonds

These are the classical covalent bonds formed by pairing of two electrons of opposite spin and are possible for all elements.
These are typical for all main group (nontransition) elements but also occur in transition metal derivatives. Because of the electronegativity differences between carbon and metals, the covalent metalā€“carbon bonds are polar MĪ“+ā€“CĪ“ā€“ covalent bonds, and the degree of polarity (percent of ionic character) depends on the electronegativity difference. The stability of polar covalent bonds is influenced by the nature of organic substituents. Electron-attracting substituents in the organic group (e.g., fluorine) increase the stability of the Mā€“C bonds. This is reflected in the fact that the Mā€“CF3 and Mā€“C6F5 derivatives are significantly thermally more stable than the nonfluorinated analogues, especially in the case of transition metals.
The stability of Ļƒ-covalent organometallic compounds is determined by thermodynamic and kinetic factors.
The main group elements form homoleptic compounds of MRn type, where n is the typical valence of the metal, which are in general thermally stable. The transition metals show less tendency to form stable homoleptic compounds; their low stability is of kinetic origin and is due to incomplete occupation of the d orbitals. Stability is gained by adding Ļ€-acceptor ligands like CO, PR3 and Ļ€-C5H5, which form additional dative bonds to increase the kinetic stability. Thus, Ti(CH3)4 is unstable at room temperature but the cyclopentadienyl derivative (Ļ€-C...

Table of contents