Ruthenium: Synthesis, Physicochemical Properties and Applications

345 Pages·2014·11.735 MB·English

by  Gary P. Keeler

CHEMISTRY RESEARCH AND APPLICATIONS

R
UTHENIUM

S , P
YNTHESIS HYSICOCHEMICAL
P A
ROPERTIES AND PPLICATIONS

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C R A
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CHEMISTRY RESEARCH AND APPLICATIONS

R
UTHENIUM

S , P
YNTHESIS HYSICOCHEMICAL
P A
ROPERTIES AND PPLICATIONS

GARY P. KEELER
EDITOR

New York
Copyright © 2014 by Nova Science Publishers, Inc.

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Library of Congress Cataloging-in-Publication Data

Ruthenium : synthesis, physicochemical properties and applications / [edited by] Gary P. Keeler.
pages cm. -- (Chemistry research and applications)
Includes bibliographical references and index.
ISBN: (cid:28)(cid:26)(cid:27)(cid:16)(cid:20)(cid:16)(cid:25)(cid:22)(cid:22)(cid:21)(cid:20)(cid:16)(cid:25)(cid:26)(cid:21)(cid:16)(cid:22) (eBook)
1. Ruthenium. I. Keeler, Gary P., editor.
QD181.R9R88 2014
546'.632--dc23
2014028265

Published by Nova Science Publishers, Inc. † New York
CONTENTS

Preface vii
Chapter 1 Solving Some of the World's Problems with Ruthenium Complexes:
Their Role in Imaging and Biomedical Applications 1
Jimmie L. Bullock, Michael J. Celestine and Alvin A. Holder
Chapter 2 Solving Some of the World's Problems with Ruthenium Complexes:
Their Use in Solar Energy Capture and Production of Hydrogen 61
Michael J. Celestine, Jimmie L. Bullock and Alvin A. Holder
Chapter 3 Advances in the Use of Ruthenium Complexes for Medicinal
Applications 91
Sarah Weisner and Shawn Swavey
Chapter 4 “RuCp” a Versatile Moiety: From NLO to Antitumor Properties 105
Tiago J. L. Silva, Paulo J. Mendes, Tânia S. Morais,
Andreia Valente, M. Paula Robalo and M. Helena Garcia
Chapter 5 Ruthenium-Catalyzed Isomerization of Allylic and Propargylic
Alcohols in Non-Conventional Solvents 165
Noel Nebra, and Joaquín García-Álvarez
Chapter 6 Voltammetric and Spectroscopic Methods
for the Ruthenium Determination in the Environment
at Ultra-Trace Concentration Level: Critical Comparison
and Application to Airborne Particulate Matter, Vegetables,
Superficial Waters, Mussels, Clams and Soils 207
Clinio Locatelli and Dora Melucci
Chapter 7 Design and Mechanistic Insight into Molecular Ruthenium-Based
Water Oxidation Catalysts 235
Markus D. Kärkäs and Björn Åkermark
Chapter 8 Ruthenium Compounds with Schiff Bases: Design and Promising
Applications of Salicylideneimine Complexes 269
Emira Kahrović
vi Contents
Chapter 9 Polymeric Ruthenium Compounds: Synthesis and Employment
As Synthons 285
Frederick P. Malan, Eric Singleton and Reinout Meijboom
Index 321
PREFACE

Ruthenium is exceedingly rare, as it is only the 74th most abundant metal on Earth. The
element is generally found in ores with the other platinum group metals in the Ural Mountains
and in North and South America. Ruthenium containing-complexes are well suited for
biological application owning to the unique properties of ruthenium. For example, ruthenium
complexes have been utilized as cellular imaging tools, radiopharmaceutical imaging tools,
and as replacements to platinum-based drugs in fighting several diseases such as cancer,
malaria, Leishmania major, and Trypanosoma cruzi, to name a few. This book discusses the
synthesis of ruthenium as well as the physicochemical properties and applications.
Chapter 1 – Ruthenium containing-complexes are well suited for biological application
owning to the unique properties of ruthenium. For example, ruthenium complexes have been
utilized as cellular imaging tools, radiopharmaceutical imaging tools, and as replacements to
platinum-based drugs in fighting several diseases such as cancer, malaria, Leishmania major,
and Trypanosoma cruzi to name a few. This chapter will discuss a brief history and
coordination chemistry of several ruthenium-containing complexes and their uses in solving
some of the world's problems.
Chapter 2 – This chapter discusses the chemistry of several ruthenium-containing
complexes and their roles in the conversion of solar energy into chemical and electrical
energy. In this chapter, subsections will include polypyridyl ruthenium dyes which are
currently being developed for their use in the manufacture of solar cells and mixed-metal and
non-mixed-metal complexes for the production of hydrogen in various media.
Chapter 3 – Transition metals and transition metal complexes have been of great value to
medicine for half a century. For example, cisplatin, cis-diaminedichloroplatinum(II), has been
a key chemotherapy drug since its FDA approval in 1978. Vanadium, chromium, and
magnesium have been proposed for many years in the treatment of diabetes. Ruthenium
complexes have been extensively studied as potential photodynamic chemotherapy drugs over
the past decade. In this chapter, the authors will review the roles played by ruthenium
coordination complexes and ruthenium organometallic complexes in the treatment of a
variety of illnesses, including uses as antimalarial, antimicrobial, and anticancer agents.
Chapter 4 – Organometallic chemistry and particularly organotransition metal complexes
have been an intensive area of research which growth was mainly motivated by the
impressive achievements in the field of homogeneous catalysis. In fact, the development of
catalysis served as foundation for many important industrial processes. Moreover, the
fascinating properties of organometallic compounds encouraged the development of its
viii Gary P. Keeler
chemistry for several other applications, ranging from material chemistry, where several
technological applications were found (integrated optics, molecular switches, dye-sensitized
solar cells (DSSCs), organic light emitting diodes (OLED’s), to bioinorganic chemistry where
they appear as potential drugs for several diseases (cancer, diabetes, malaria, etc.). In this
frame, ruthenium organometallic complexes have revealed a prominent role in all these areas
due to their great scope in molecular engineering. The vast diversity of frameworks and
structures, associated with their stability in several oxidation states, bonding modes and
electronic features place ruthenium compounds among the most successful organotransition
metal complexes studied to date. In particular, η5-monocyclopentadienylruthenium
derivatives (“RuCp”) have been thoroughly studied due to the promising results in the field of
nonlinear optics. More recently, the “RuCp” fragment emerged in the new fascinating
bioorganometallic subject, displaying important results in the area of potential agents for
cancer therapy. These apparent greatly incongruent endeavors might find some common
explanation in the unique characteristics of this versatile metal fragment. This chapter
presents an overview of the work published during the last two decades in the fields of
nonlinear optics and bioorganometallic chemistry concerning the “RuCp” scaffold. An
outlook of the synthetic methods involved and the relevant properties for each purpose is also
discussed. It will be shown the versatility of the “RuCp” on the design of different
organometallic environments, with structural features aiming a particular application.
Chapter 5 – In this contribution, the catalytic activity of a plethora of ruthenium
complexes in the isomerization of allylic and propargylic alcohols in non-conventional
solvents [water, ionic liquids (ILs), glycerol and Deep Eutectic Solvents (DESs)] is reviewed.
On the one hand, the search for organic reactions proceeding with efficiency, selectivity and
atom economy has emerged as a prime goal in synthetic chemistry. Among the organic
reactions that proceed with atom economy, isomerization reactions are typical examples
because no by-products are generated. To this regard, the ruthenium-catalyzed isomerizations
of readily accessible allylic and propargylic alcohols, mainly giving carbonyl compounds,
provide a simple synthetic route to these very valuable raw materials in organic chemistry. On
the other hand, combination of ruthenium-catalyzed isomerization reactions and non-
conventional solvents has led in recent years to the development of a huge number of new and
greener synthetic methodologies. In this chapter, an overview of the progress achieved on the
ruthenium-catalyzed isomerization of allylic and propargylic alcohols in environmentally-
friendly solvents will be presented, with special emphasis on synthetic applications.
Chapter 6 – The problem related to the presence of Platinum Group Metals (PGMs) in the
environment has raised much attention and great interest in the scientific community. This is
due to the fact that the PGMs are widely used in various fields, such as anticancer drugs,
jewels production, photographic operations, industrial catalysts, and especially autocatalytic
converters. In the last case, their continuous use and deterioration implies a considerable
release of these metals in the environment. It should be noted that the metals initially used in
autocatalytic converters were platinum, palladium and rhodium, but in recent years such
PGMs were gradually and partially replaced, or alloyed with osmium and especially
ruthenium. Their addition in the manufacture of autocatalytic converters helps them withstand
high temperatures and wear, thus increasing the product life. Thus, the increasing use of
autocatalytic converters shows two decidedly conflictual effects on the environment: an
evident and drastic reduction of the concentration levels of lead, and, at the same time, an
equally evident and widespread increase of the PGMs concentration, and in particular of