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Probing ground and excited state properties of Ruthenium(II) and
Osmium(II) polypyridyl complexes

Wesley R. Browne
A Thesis presented to Dublin City
University for the degree of Doctor of
Philosophy.

2002

Probing ground and excited state properties of
Ruthenium(II) and Osmium(II) polypyridyl complexes

Isotope, pH, solvent and temperature effects.

by

Wesley R. Browne, BSc.(Hons), AMRSC
A Thesis presented to Dublin City University for the degree of
Doctor of Philosophy.

Supervisor: Professor Johannes G. Vos
School of Chemical Sciences
Dublin City University

August 2002
Dedicated to Matthew & to the memory of Ross and Mick

“Caste a cold eye on life, on death.
Horseman pass by”

Epitaphf o r W illiam Butler Yeats

REFERENCE

I hereby certify that this material, which I now submit for assessment on the programme of study leading to the award of Doctor of Philosophy by research and thesis, is entirely my own work and has not been taken from work of others, save and to the extent that such work has been cited within the text of my work.

I D. No. 95478965 Date:_______ (( / Û /

iv

Abstract

The area of ruthenium(H) and osmium(H) polypyridyl chemistry has been the subject of intense investigation over the last half century. In chapter 1, topics relevant to the studies presented in this thesis are introduced. These areas include the basic principles behind the ground and excited state properties of Ru(II) and Os(II) polypyridyl complexes, complexes incorporating the 1,2,4-triazole moiety and the application of deuteriation to inorganic photophysics.

Chapter 2 details experimental and basic synthetic procedures employed in the studies presented in later chapters. A limited discussion of practical aspects of both synthetic procedures and physical measurements is included, in particular where major difficulties were encountered and where improvements to standard procedures were made.

A central theme to this thesis is the application of deuteriation as a spectroscopic probe. In order to fully exploit its potential fully, a general and systematic approach to the deuteriation of polypyridyl type ligands is required. In chapter 3 a range of isotopomers of heteroaromatic compounds containing pyrazyl-, pyridyl-, 1,2,4-triazole-, thienyl-, methyl-, and phenyl- moieties, are reported.

The application of deuteriation in inorganic chemistry as a spectroscopic probe both in simplification of NMR and Raman spectra and as a probe into the excited state structure of heteroleptic complexes is the focus of chapter 4. Deuteriation is employed extensively to probe the excited state structure of several series of Ru(II) and Os(II) polypyridyl complexes. In particular the effect of deuteriation on emission lifetime and ground and excited state resonance Raman spectra is investigated.

In chapter 5, the phenomena of temperature dependent dual luminescence observed for the mononuclear complex [Ru(bpy)2 (pztr)]+ forms the basis of a wider investigation of related complexes in an effort to gain more insight into the nature of the phenomenon. In addition some fundamental studies into the picosecond excited state processes of [Ru(bpy)3]2+are presented. In these studies deuteriation shows itself as a powerful tool in effecting small but important perturbations.

In Chapter 6 the separation, characterisation and photophysical properties of the stereoisomers of mono- and bi-nuclear Ru(II) polypyridyl complexes is examined. In particular the importance of chirality both in terms of solvent and in complex in determining the circular dichroism, ]H NMR spectroscopy and photophysical properties is investigated.

In chapters 7 and 8, attention is turned to binuclear systems incorporating 1,2,4-triazole moieties. The effects of variations in the bridging ligand in these systems (e.g., distance and spacer groups, pyrazine vs. triazole etc.) are examined. Deuteriation is employed in some of these systems as a tool in assessing the localisation of the lowest emissive excited state on particular moieties of the complexes.

v

Acknowledgements

Where do I start! A t the beginning I suppose. M y Family: Thank you Mum for unrelenting support throughout that epic 21 year quest

that is known as an education and for the many heated discussions we have had over those years. I won’t forget it in your twilight years (I am sure I will be able to arrange a job in an old folks home for you). To my sister “Garda Nicola Browne” for always being there for me, despite the fact I manage to get on your nerves without even trying. Next to Mick for all the trouble you’ve caused in the few years I have known you (namely Ross and Matthew), thank you for being a friend; you are not forgotten. To Ross, whom is always there like the warm glow of an open hearth. And last but by no means least to Matthew for being, well, Matthew, the ultimate in long-lived excited states.

M y Mentors', the main man, Han, the boss, a.k.a Prof. J.G. Vos. The first day I started my postgrad you said something that set the tone for the following three years- “0 / course

you can harass me - but come in and close the door first”. And it went downhill after

that. Thanks for the enthusiasm, interest and encouragement over the years and for the freedom to do what I was interested in. Also thanks Ronald (Dr. Ronald Hage), for convincing me to do a Phd in the first place and for being the perfect boss (i.e. leaving me alone to get on with it; must be a dutch trait). And finally to my Sensei (Mr. John Sweeney) for teaching me self-discipline, how to be a true martial artist and for keeping me focused through my teenage years.

M y friends in the North. Firstly to Prof. J.J. McGarvey for allowing me to use his Raman

facilities at Queen’s University Belfast and sending me to R.A.L.. Thanks Colin (take a break) Coates and Clare (how did you survive the years with Colin!!) Brady. Oh, and thanks Pavel, Mike and Stan with those ultrafast thingies. And also to Kate, Ali and Murph for making Belfast more welcoming.

On the International seen: Bologna, Italy - Firstly thanks to Mama (Prof) Teresa and Papa (Prof) Roberto for helping me learn something about real photophysics and for making me feel welcome on my visits to Bologna. To the family Passaniti, for putting me up in Bologna and for welcoming me with open arms. And to Paolo, a gentleman and a scholar (and a stirrer if ever there was one). To Cincia and Sebastiano in Messina thanks for an interesting adventure that was the DPY/DPZ saga! To Dr. Dusan Hesek and Dr. Claudio Villani (maybe we will actually meet some day) for help with chiral separations.

My proof readers Jennifer McKenna and Aine Connolly (you didn’t know what you were letting yourselves in for!). This thesis would not have read near as good without your help. As for the mistakes still in it, I take full responsibility as they are entirely my own (and Han’s).

Thanks also go Sligo VEC and Enterprise Ireland for helping me out with a few quid over the years and to the SCS for the facilities in which to do the work.

On the Technical side; I would like to thank all the technicians in the School of Chemical Sciences for being the most capable and professional group of people I will probably ever have the pleasure of working with. My thanks to Mick (an all round good egg if ever their was one), Maurice (Jim‘ill fix it for you), Damien (scuba boy), Veronica and Ann (for

vi sorting out the mess that is the ordering system and more importantly the mess I usually made of it), Ambrose, Vinny, John, Mary and Tony.

On the staf f s ide, I thank especially Dr. Mary Pryce, Dr. Paraic James, Dr. Peter Kenny, Dr John Gallagher, Dr. Josh Howarth and Dr. Kieran Nolan for the invaluable advice they have given over the years.

On the PGAC side, Prof. Malcolm Smyth, Prof. Robert Forster, Mick Burke (again!) Kathleen Greenan, Ger McDermott, Marion King, Jennifer Brennan, Dr. Brett Paul and Dr Dermot Brougham. It was an interesting experience that I am thankfully none the worse for. Keep up the good work.

Myfriends/colleagues- there are too many to name but a few bear special mention: Firstly, in the HVRG past and present, again in no particular order. Dr Christine (have you got another paper written for me yet) O’Connor (is it D.O’C or C.O’C), Dr Francis Weldon, Dr Luke O’Brien, Dr. J. Scott Killeen, thanks for getting me started. To Adrian, Dec, Helen and Marco - I could not have done it without you, good luck in the future. I must point out that both Adrian and Dec are in no small measure responsible for me being able to work with purish compounds, thanks for the help lads. Marco deserves an extra mention (if only for his hair’s chameleon properties), thanks for challenging my thoughts and interpretations not just in chemistry. Thanks to Gillian Whitaker for helping me (doing the donkey work) on the osmium monomers. Also thanks to Carl and Jennifer, who have managed to stay friends with me for SEVEN years, that’s staying power. Oh, and thanks Noel for the CHN’s and for proving chemistry can be amusing, and Clare (where’s my paper) Brennan for making purple the new orange!

My closest (non-chemistry)   friends, in no particular order, Aine Connolly, Lorraine

O’Reilly, Alan Pearson, Ed Walsh, Jupe Van den Broeke (technically your chemistry but I’ve never seen you do anything so the jury is still out), Tom Roberts, Fenton Ewing, Gareth Wynne. Thanks for helping me over the years.

My undergrad days', those were Halcyon days, thanks to thatAC shower! Hopefully we will stay in touch.

And last I guess I should mention my housemates in Albert College park. Mark (physics), Kevin (Chemistry), and Henry (biology). It has been an interesting few years. Thankfully in the good sense. Thanks also to Phyllis (my Clare mother) and the girls! in Santry and Fran (I vont to be aloon) in Beaumont

And to the people I haven ’ t m entioned, I have done soon purpose (I’ve got writers cramp

and there are too many of you).

Table of contents

Titl e p ages Abstract

iv

Acknowledgements Table ofcontents Glossary

vi viii x

  • Chapter 1
  • Introduction

Introduction Supramolecular chemistry Group VIII photophysics

1

234
20
1.0 1.1 1.2

  • 1.3
  • 1,2,4-triazole based heteroleptic Ru(II) and Os(II)

complexes

studies
1.5 1.6
Scope of thesis Bibliography
55 56

  • Chapter 2
  • General introduction to synthetic and purification

procedures, physical techniques and measurements

General synthetic procedures and considerations Chromatographic techniques Nuclear Magnetic Resonance spectroscopy Electronic spectroscopy Time Correlated Single Photon counting (TCPSC) techniques, nanosecond and picosecond time resolved emission spectroscopy

63

2.1 2.2 2.3 2.4 2.5
64 73 74 79 85

spectroscopy
87
2.7 2.8 2.9
2.10 2.11
Mass spectrometry Photochemical studies Electrochemical measurements Elemental Analysis
89 89 89 90

compounds

Introduction Results Discussion Conclusions Experimental Bibliography
3.1 3.2 3.3 3.4 3.5 3.6
94 98
100 109 109 116

  • Chapter 4
  • Probing excited state electronic structure of monomeric
  • 120

Ru(II) and Os(II) tris heteroleptic complexes by selective deuteriation

Introduction Resultsand Discussion Conclusions Experimental Bibliography
4.1 4.2 4.3 4.4 4.5
121 126 142 143 143

viii

145
Temperature and time resolved emission properties of mononuclear Fe(II) and Ru(II) polypyridyl complexes

Introduction Resultsand Discussion Conclusions Experimental Bibliography

Chapter 5

5.1
146 155 169 170 170
5.2 5.3 5.4 5.5

  • 174
  • Separation and photophysical properties of the
  • Chapter 6

stereoisomers of mono- and binuclear Ru(II) complexes

Introduction Resultsand Discussion Concluding remarks Experimental
175 177 185 186 186
6.1 6.2 6.3 6.4

  • 6.5
  • Bibliography

  • 189
  • Binuclear Ruthenium complexes - controlling ground
  • Chapter 7

state interactions

Introduction Results
190 197 207 211 212 213
7.1 7.2 7.3 7.4 7.5 7.6
Discussion Conclusions Experimental Bibliography

  • 216
  • The Creutz-Taube ion revisited - Binuclear complexes
  • Chapter 8

containing non-bridging 1,2,4-triazole moieties

217 220 231 235 236 237
Introduction Results Discussion Conclusions and outlook Experimental Bibliography
8.1 8.2 8.3 8.4 8.5 8.6

239

240 243

  • Chapter 9
  • Conclusions and Future work

Conclusions Future work
9.1 9.2

Appendices

Appendix A Posters, presentations and publications Appendix B Ground state resonance Raman spectra

Appendix C Excited state resonance Raman spectra

Appendix D Temperature and time resolved emission spectra

Appendix E Hush theory and classification of mixed valence complexes Appendix F Synthesis and characterisation of Ru(II) and Os(II) polypyridyl complexes

Glossary
Abbreviations used throughout this thesis

  • CD
  • Circular Dichroism

COSY CSFE CT

CT

FC
Correlated spectroscopy crystal field stabilization energy Charge Transfer

n6+

  • ]'
  • Creutz Taube ion: [(NH3

Franck-Condon

  • )
  • 5Ru(|a-pz)Ru(N
  • 1^

3
)5

  • GS
  • Ground state

HMBC HMQC HOMO IT/MMCT LUMO !MLCT 3MLCT ^ C /'d d
Heteronuclear multiple bond coherence Heteronuclear multiple quantum coherence Highest occupied molecular orbital Intervalence Transition/ metal to metal charge transfer Lowest unoccupied molecular orbital singlet metal to ligand charge transfer state triplet metal to ligand charge transfer state singlet metal centred

3

  • MC/3dd
  • triplet metal centred

NOE OTTLE PMD’s
Nuclear Overhauser Effect enhancement Optically transparent thin layer electrode Photomolecular devices tt-7i*/IL/LC intraligand or ligand centred transition CTTS S
Charge transfer to solvent Huang Rhys Factor

  • SCE
  • supercritical fluid H/D exchange (Chapter 3 only)

  • SCE
  • Saturated Calomel electrode (all chapters except chapter 3)

vide infra vide supra see below see above

N.B. For the ruthenium(II) complex based on the ligand Hppt the abbreviations pptland ppt2 refer to the binding mode.

Refers to binding via N1 oftriazole and pyridine Refers to binding via N2 of triazole and pyrazine pptl PPt2

Abbreviations and molecular structures of compounds discussed in this thesis

2

,

2

’-bipyridine bpy

  • 4,4’-bpy
  • 4,4’-bipyridine

2,2’-bipyridine-N,N’-dioxide 4,4’-dicarboxy-2,2’-bipyridine 4,4’-dimethyl-2,2’-bipyridine 4,4’-diphenyl-2,2’-bipyridine
2,2’-bpy-N,N-dioxide H2dcb dmb dpb

1

,1 0 -phenanthroline
4,7-diphenyl-l,10-phenanthroline
’-biquinoline phen ph2phen biq

2
,2

2,3-bis(pyrid-2’-yl)-pyrazine

2 , 2 ’;6 , 2 ’-terpyridine

dpp terpy

2

  • -(thien- 2 ’-yl)-pyridine
  • pyth

2

-(phenyl)-pyridine

ppy

2-(pyridin-2’-yl)-pyrazine dipyridophenazine pypz dppz

  • 1,10-Phenanthroline-5,6-dione
  • phi

  • 2,2’-dipyridyl-amine
  • HDPA

Hpytr Hpztr HMepytr HMepztr 1-Mepytr 1-Mepztr Hphpytr Hphpztr Htolpztr Hbpt
3-(pyridin-2’-yl)-1H-1,2,4-triazole 3-(pyrazin-2’-yl)-1H-1,2,4-triazole 5-methyl-3-(pyridin-2’-yl)-1H-1,2,4-triazole 5-methyl-3-(pyrazin-2’-yl)-1H-1,2,4-triazole 1-methyl-3-(pyridin-2’-yl)-1H-1,2,4-triazole 1-methyl-3-(pyrazin-2’-yl)-1H-1,2,4-triazole 5-phenyl-3-(pyridin-2’-yl)-1H-1,2,4-triazole 5-phenyl-3-(pyrazin-2’-yl)-1H-1,2,4-triazole 5-toluyl-3-(pyrazin-2’-yl)-1H-1,2,4-triazole 3,5-bis(pyridin-2’-yl)-lH-l,2,4-triazole 3,5-bis(pyrazin-2’-yl)-1H-1,2,4-triazole 3-(pyrazin-2’-yl)-5-(pyridin-2’-yl)-1H-1,2,4-triazole
Hbpzt Hppt

N= /
R1

  • H
  • bpy
  • =

R

2

dmb = CH3

  • phen
  • =
  • H

  • dpb = phenyl
  • ph2phen = phenyl

Q-O

o

2,2'-bpy-/V/V'-dioxide

a t)

N

S 1

  • pypz
  • HDPA

pyth

ppy

N = \

N=v N.
/- n

C W T

N '

v / ~ <ch2:

i

H
R3
1-Mepytr = CH 1-Mepztr = N

  • Hpztr
  • =
  • H

4,4-bpy n =0
R4

= H
HMepztr = methyl Hphpztr = phenyl Htolpztr = p-tolyl Hbpzt Hppt

  • P2P
  • n = 2

Hpytr

HMepytr = methyl Hphpytr =phenyl
= pyrazinyl

= pyridinyl

  • Hbpt
  • = pyridyl-

/¡ — X.

x=

c y

Me H
N=.

? II

'rVvN=w v

.S,

H

h -N . N

N 'N'H

W I F

H

HjtMetrJ^z

X
H2(pytr)2th = CH

H2(pztr)2th = N
Hpytrth * CH Hpztrth = N

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  • Designing Ruthenium Anticancer Drugs: What Have We Learnt from the Key Drug Candidates?

    Designing Ruthenium Anticancer Drugs: What Have We Learnt from the Key Drug Candidates?

    inorganics Review Designing Ruthenium Anticancer Drugs: What Have We Learnt from the Key Drug Candidates? James P. C. Coverdale 1 , Thaisa Laroiya-McCarron 2 and Isolda Romero-Canelón 2,* 1 Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK; [email protected] 2 School of Pharmacy, Institute of Clinical Sciences, University of Birmingham, Birmingham B15 2TT, UK; [email protected] * Correspondence: [email protected] Received: 29 November 2018; Accepted: 13 February 2019; Published: 1 March 2019 Abstract: After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro activity; however, we have yet to find a ruthenium complex that would be a viable alternative to platinum drugs currently used in the clinic. We aimed to explore what we have learned from the most prominent complexes in the area, and to challenge new concepts in chemical design. Particularly relevant are studies involving NKP1339, NAMI-A, RM175, and RAPTA-C, which have paved the way for current research. We explored the development of the ruthenium anticancer field considering that the mechanism of action of complexes no longer focuses solely on DNA interactions, but explores a diverse range of cellular targets involving multiple chemical strategies. Keywords: ruthenium; anticancer; metal complex 1. Introduction Cancer is a major health burden in the developed world. Although many breakthroughs in biological targeted approaches have occurred (specifically, immunological therapy), an unmet clinical need remains for a large section of the patient population, so wide-spectrum chemotherapy agents are still required.
  • Periodic Table 1 Periodic Table

    Periodic Table 1 Periodic Table

    Periodic table 1 Periodic table This article is about the table used in chemistry. For other uses, see Periodic table (disambiguation). The periodic table is a tabular arrangement of the chemical elements, organized on the basis of their atomic numbers (numbers of protons in the nucleus), electron configurations , and recurring chemical properties. Elements are presented in order of increasing atomic number, which is typically listed with the chemical symbol in each box. The standard form of the table consists of a grid of elements laid out in 18 columns and 7 Standard 18-column form of the periodic table. For the color legend, see section Layout, rows, with a double row of elements under the larger table. below that. The table can also be deconstructed into four rectangular blocks: the s-block to the left, the p-block to the right, the d-block in the middle, and the f-block below that. The rows of the table are called periods; the columns are called groups, with some of these having names such as halogens or noble gases. Since, by definition, a periodic table incorporates recurring trends, any such table can be used to derive relationships between the properties of the elements and predict the properties of new, yet to be discovered or synthesized, elements. As a result, a periodic table—whether in the standard form or some other variant—provides a useful framework for analyzing chemical behavior, and such tables are widely used in chemistry and other sciences. Although precursors exist, Dmitri Mendeleev is generally credited with the publication, in 1869, of the first widely recognized periodic table.
  • Syntheses, Crystal Structures and Magnetic Properties of Rb Ruo and K

    Syntheses, Crystal Structures and Magnetic Properties of Rb Ruo and K

    Syntheses, Crystal Structures and Magnetic Properties of Rb2RuO4 and K2RuO4 Dieter Fischera, Rudolf Hoppeb, Kailash M. Mogarea, and Martin Jansena a Stuttgart, Max-Planck-Institut f¨ur Festk¨orperforschung, Heisenbergstraße 1, D-70569 Stuttgart, Germany b Institut f¨ur Anorganische und Analytische Chemie, Heinrich-Buff-Ring 58, D-35392 Gießen, Germany Reprint requests to Prof. Dr. Martin Jansen. Fax: +49-711/6891502. E-mail: [email protected] Z. Naturforsch. 60b, 1113 – 1117 (2005); received August 23, 2005 Potassium and rubidium oxoruthenates, A2RuO4, were synthesized from the alkali perox- ides/hyperoxides and ruthenium dioxide. Both compounds crystallize in the orthorhombic space group Pnma (no. 62), (K2RuO4: a = 7.673(2), b = 6.153(2) and c = 10.564(3) A,˚ Z = 4, 796 unique reflections, R = 3.5%; Rb2RuO4: a = 8.106(2), b = 6.270(1) and c = 11.039(2) A,˚ Z = 4, 889 unique reflections, R = 3.6%). The crystal structures, as determined from single crystal data, are of the β- K2SO4 type. Magnetic measurements reveal that both compounds are paramagnetic down to tem- peratures of around 60 K and further exhibit antiferromagnetic transitions, at around TN = 9 K for Rb2RuO4, and two transitions with TN = 14 K and 4 K for K2RuO4. The magnetic moments as de- termined applying Curie-Weiss law for both compounds are 2.68 µB, thus confirming the oxidation state +6 of ruthenium. Key words: Potassium and Rubidium Oxoruthenates, Ruthenium, Crystal Structure, Magnetic Properties Introduction the syntheses, crystal structure and magnetic properties of K2RuO4 and Rb2RuO4. Ruthenates crystallize in a rich variety of struc- ture types ranging from pyrochlores and hollandites Experimental Section to perovskite type phases, and exhibiting interesting Syntheses magnetic and electronic properties.
  • Metal-Ligand Exchange Kinetics in Platinum and Ruthenium Complexes SIGNIFICANCE for EFFECTIVENESS AS ANTICANCER DRUGS

    Metal-Ligand Exchange Kinetics in Platinum and Ruthenium Complexes SIGNIFICANCE for EFFECTIVENESS AS ANTICANCER DRUGS

    DOI: 10.1595/147106708X255987 Metal-Ligand Exchange Kinetics in Platinum and Ruthenium Complexes SIGNIFICANCE FOR EFFECTIVENESS AS ANTICANCER DRUGS By Jan Reedijk Leiden Institute of Chemistry, PO Box 9502, 2300 RA, Leiden, The Netherlands; E-mail: [email protected] Metal coordination compounds with ‘slow’metal-ligand exchange rates, comparable to those of cell division processes, often appear to be highly active in killing cancer cell lines. This is particularly marked in platinum and ruthenium complexes. Classical examples such as cisplatin, as well as very recent examples from the author’s and other work, will be discussed in detail, and in the context of the current knowledge of the mechanism of antitumour action. It is shown that even though much is known about the molecular mechanism of action of cisplatin, many challenging questions are left for future research. For the ruthenium anticancer drugs molecular mechanistic studies are only at the beginning. Mechanistic studies on both platinum and ruthenium compounds have, however, opened many new avenues of research that may lead to the design of completely new drugs. Since the appearance of the early review on cis- O O diamminedichloridoplatinum(II), commonly known NH2 Pt as cisplatin, 1, in this Journal (1), and its early success- NH2 es in the treatment of a variety of tumours, the topics O O of metal-DNA binding and platinum antitumour 3 Oxaliplatin chemistry have attracted considerable interest from chemists, pharmacologists, biochemists, biologists action of cisplatin and related drugs. This knowledge and medical researchers (2). In fact cisplatin and the has clearly resulted in much improved clinical later compounds carboplatin, 2, and oxaliplatin, 3, administration protocols, as well as motivated enjoy the status of the world’s best-selling anticancer research on other, related drugs containing transition drugs.
  • Ruthenium Melt Catalysis PRODUCING CHEMICALS from SYNTHESIS GAS by John F

    Ruthenium Melt Catalysis PRODUCING CHEMICALS from SYNTHESIS GAS by John F

    Ruthenium Melt Catalysis PRODUCING CHEMICALS FROM SYNTHESIS GAS By John F. Knifton Texaco Chemical Company, Austin, Texas A range of commodity chemicals and fuels can be generated directly from synthesis gas by ruthenium melt catalysis. Careful selection of the catalyst components enables a wide range of oxygenates to be produced, while other advantages of this flexible process include high productivity and the ease with which the products may be recovered and the catalyst recycled. In platinum-metal catalysed organic syn- present a renewable surface may avoid many of thesis, the primary purpose is to produce pure the problems of deactivation seen with con- products in high yields, with good ventional heterogeneous catalysts (4). reproducibility and ease of product isolation. Frequently, the melt is called upon to play While both homogeneous and heterogeneous more than one role in a chemical process. It catalysis systems may fulfill these roles in may, for example, simply act as a solvent for laboratory or industrial processes, an alterna- reactants and products; it may be a catalyst; it tive approach, that has many of the inherent may supply one or more of the reactants, as well advantages of both systems, is the use of molten as aid in controlling the heat of reaction. The salts as catalyst and/or reaction media. salts may be used singly (for example molten Molten salts may be classified into simple Na2C03, ZnCL or AlC13), or as eutectic ionic salts (for example the alkali and alkaline mixtures (such as Li2C03-Na2C03-K2C03, earth metal halides), simple and polymeric CuC1-CuCl2-KC1, and AlC13-BuPyC1) where oxyanionic salts (such as metal nitrates, car- the lower liquidus temperatures may be bonates, phosphates, borates), and salts contain- advantageous.
  • Periodic Table P J STEWART / SCIENCE PHOTO LIBRARY PHOTO SCIENCE / STEWART J P

    Periodic Table P J STEWART / SCIENCE PHOTO LIBRARY PHOTO SCIENCE / STEWART J P

    Periodic table P J STEWART / SCIENCE PHOTO LIBRARY PHOTO SCIENCE / STEWART J P 46 | Chemistry World | March 2009 www.chemistryworld.org Periodic change The periodic table, cherished by generations of chemists, has steadily evolved over time. Eric Scerri is among those now calling for drastic change The periodic table has become recurrences as vertical columns or something of a style icon while In short groups. remaining indispensable to chemists. In its original form The notion of chemical reactivity Over the years the table has had the periodic table was is something of a vague one. To make to change to accommodate new relatively simple. Over this idea more precise, the periodic elements. But some scientists the years, extra elements table pioneers focused on the propose giving the table a makeover have been added and the maximum valence of each element while others call for drastic changes layout of the transition and looked for similarities among to its core structure. elements altered these quantities (see Mendeleev’s More than 1000 periodic systems Some call for drastic table, p48). have been published since the table rearrangements, The method works very well for Russian chemist Dimitri Mendeleev perhaps placing hydrogen the elements up to atomic weight developed the mature periodic with the halogens. 55 (manganese) after which point system – the most fundamental A new block may be it starts to fall apart. Although natural system of classification needed when chemists there seems to be a repetition in the ever devised. (Not to mention the can make elements in highest valence of aluminium and hundreds if not thousands of new the g-block, starting at scandium (3), silicon and titanium systems that have appeared since the element 121 (4), phosphorus and vanadium (5), advent of the internet.) and chlorine and manganese (7), Such a proliferation prompts this is not the case with potassium questions as to whether some tables and iron.