NOx Related Chemistry

1. Auflage 2015
ISBN: 978-0-12-801837-8
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, Band Volume 67, 388 Seiten

Reihe: Advances in Inorganic Chemistry

NOx Related Chemistry is a volume of a series that presents timely and informative summaries of the current progress in a variety of subject areas within inorganic chemistry, ranging from bio-inorganic to solid state studies. This acclaimed serial features reviews written by experts in the field and serves as an indispensable reference to advanced researchers. Each volume contains an index, and each chapter is fully referenced. - Best-qualified scientists write on their own recent results dealing with basic fundamentals of NO-chemistry, with an eye into biological and environmental issues - Editors and authors are recognized scientists in the field - Features comprehensive reviews on the latest developments - An indispensable reference to advanced researchers

Autoren/Hrsg.

Inhaltsverzeichnis

1;Front Cover;1
2;NOx Related Chemistry;4
3;Copyright;5
4;Contents;6
5;Contributors;10
6;Preface;12
7;Chapter One: NOx Linkage Isomerization in Metal Complexes;14
7.1;1. Introduction;15
7.1.1;1.1. Modes of binding of NOx moieties in monometallic complexes;16
7.1.1.1;1.1.1. Nitric oxide complexes;16
7.1.1.2;1.1.2. NO2 complexes;17
7.1.1.3;1.1.3. NO3 complexes;18
7.1.2;1.2. Methods that induce linkage isomerization;18
7.1.3;1.3. Techniques for detecting linkage isomers;18
7.1.4;1.4. Factors that affect linkage isomerization;19
7.2;2. Linkage Isomerism in Non-Porphyrin NOx Complexes;20
7.2.1;2.1. Group 6 (Cr and Mo) complexes;20
7.2.1.1;2.1.1. NO complexes;20
7.2.1.2;2.1.2. NO2 complexes;23
7.2.2;2.2. Group 7 (Mn and Re) complexes;24
7.2.2.1;2.2.1. NO complexes;24
7.2.3;2.3. Group 8 (Fe, Ru, and Os) complexes;26
7.2.3.1;2.3.1. NO complexes;26
7.2.3.2;2.3.2. NO2 complexes;31
7.2.3.3;2.3.3. NO3 complexes;33
7.2.4;2.4. Group 9 (Co, Rh, and Ir) complexes;34
7.2.4.1;2.4.1. NO complexes;34
7.2.4.2;2.4.2. NO2 complexes;35
7.2.5;2.5. Group 10 (Ni, Pd, and Pt) complexes;36
7.2.5.1;2.5.1. NO complexes;36
7.2.5.2;2.5.2. NO2 complexes;38
7.3;3. Linkage Isomerism in NOx-Coordinated Metalloporphyrins;41
7.3.1;3.1. Manganese NOx porphyrins;42
7.3.2;3.2. Ruthenium and iron NOx porphyrin complexes;50
7.3.3;3.3. Cobalt NOx porphyrins;58
7.3.4;3.4. Hyponitrite complexes of transition metal porphyrins;60
7.3.4.1;3.4.1. The nitric oxide dimer and its reduced forms;64
7.3.4.2;3.4.2. Metal hyponitrite binding modes;67
7.3.5;3.5. Heme proteins;83
7.4;4. Conclusion;91
7.5;Acknowledgment;91
7.6;References;91
8;Chapter Two: Three Redox States of Metallonitrosyls in Aqueous Solution;100
8.1;1. Introduction: General Scope;101
8.2;2. Complexes with n=6;102
8.2.1;2.1. Structure, spectroscopy, and electronic description. Total spin S=0. Dominant M–NO+ distribution;102
8.2.1.1;2.1.1. Significance and importance of the ``back-bonding model´´;104
8.2.1.2;2.1.2. Role of the s*-FeNO interaction in the trans-effect exerted over NO;106
8.2.1.3;2.1.3. ``Negative´´ trans-influence of the nitrosyl moiety;107
8.2.1.4;2.1.4. Different reactivity of the L ligand trans to NO;108
8.2.1.5;2.1.5. Other metal centers: Validity of the formal charge descriptions;108
8.2.1.6;2.1.6. Frontier MOs;109
8.2.2;2.2. Formation and dissociation of NO-complexes: Nitrosylations and denitrosylations;109
8.2.2.1;2.2.1. Reactions with M(II) precursors (M=Fe, Ru): Proton-assisted dehydration of bound nitrite;109
8.2.2.2;2.2.2. Reactions with high-spin M(III) precursors;110
8.2.2.3;2.2.3. Reactions with low-spin, nonheme Fe(III) systems;110
8.2.2.4;2.2.4. Nitrosylation of nitrile-hydratase and models;112
8.2.2.5;2.2.5. Nitrosylation of low-spin Fe(III)-heme models, [FeIII(TMPS)(CN)(H2O)]4- and [FeIII(TMPS)(CN)2]5-;114
8.2.2.6;2.2.6. Nitrosylations of other [FeIII(CN)5(Y)]n- complexes;115
8.2.2.7;2.2.7. Nitrosylations with Ru(III) precursors;116
8.2.2.8;2.2.8. Why is the release of NO so fast for the {FeIINO+} heme-nitrosyls?;117
8.2.3;2.3. Electrophilic reactivity toward O-, N-, and S-binding nucleophiles;118
8.2.3.1;2.3.1. General approach to electrophilic reactivity;118
8.2.3.2;2.3.2. Correlation of nucleophilic rates with M(NO+)/M(NO) redox potentials;120
8.3;3. Complexes with n=7;121
8.3.1;3.1. Structure, spectroscopy, and electronic descriptions for 5- and 6-coordination. Total spin S=1/2 or 3/2. Alternative...;121
8.3.1.1;3.1.1. Heme and nonheme 5C nitrosyls with S=1/2;121
8.3.1.2;3.1.2. Nonheme and heme 6C nitrosyls with S=1/2;125
8.3.1.3;3.1.3. Nonheme nitrosyls with S=3/2;127
8.3.2;3.2. The trans-effect in heme- and nonheme complexes;127
8.3.3;3.3. Formation and dissociation of NO-complexes: Disproportionation reactions;128
8.3.3.1;3.3.1. Nitrosylations;128
8.3.3.2;3.3.2. Dinitrosyl complexes and disproportionation reactions;129
8.3.4;3.4. Nucleophilic reactivity: The reactions of [ML5(NO)]n with oxygen;133
8.4;4. Complexes with n=8;136
8.4.1;4.1. Structure, spectroscopy, and electronic description: Dominant 1NO-/1HNO (S=0);136
8.4.1.1;4.1.1. NO--complexes;136
8.4.1.2;4.1.2. HNO-complexes;139
8.4.2;4.2. Characterization of the NO-/HNO interconversions in solution;142
8.4.3;4.3. A potential-pH diagram in aqueous solution for the different complexes based on the [Ru(Me3[9]aneN3)(bpy)]2+ fragment;145
8.4.4;4.4. Comparative reactivity of NO- and HNO complexes;146
8.4.4.1;4.4.1. Ligand exchange in solution;146
8.4.4.2;4.4.2. Redox reactivity;147
8.4.5;4.5. Nucleophilic reactivity: The reactions with dioxygen;149
8.5;5. Conclusions;149
8.6;References;150
9;Chapter Three: Recent Progress in Photoinduced NO Delivery With Designed Ruthenium Nitrosyl Complexes;158
9.1;1. Introduction;158
9.2;2. Photoactive Ru Nitrosyls: What We Knew Before Our Work;163
9.3;3. Photoactive {RuNO}6 Nitrosyls Derived from Pentadentate Polypyridine Ligands;165
9.4;4. Tuning the Photosensitivity of Ru Nitrosyls to Light of Longer Wavelengths;168
9.5;5. Incorporation of Ru Nitrosyls into Polymeric Matrices;172
9.6;6. Enhancement of Light Absorption of {Ru-NO}6 Nitrosyls Through Direct Attachment of Dyes;173
9.7;7. Conclusion;180
9.8;Acknowledgments;181
9.9;References;181
10;Chapter Four: Metal-Assisted Activation of Nitric Oxide—Mechanistic Aspects of Complex Nitrosylation Processes;184
10.1;1. Introduction;185
10.2;2. Nitric Oxide Activation by Iron(II)/(III) Centers;186
10.2.1;2.1. Nitric oxide activation by synthetic iron(III) porphyrins and hemoproteins;186
10.2.1.1;2.1.1. Nitric oxide binding to simple iron(III) porphyrin models;187
10.2.1.2;2.1.2. Interactions of nitric oxide with highly charged iron(III) porphyrins;194
10.2.1.3;2.1.3. Nitric oxide reactivity toward P450 functional models;199
10.2.1.4;2.1.4. Nitric oxide activation by selected hemoproteins;204
10.2.1.4.1;2.1.4.1. Nitric oxide binding to P450cam;204
10.2.1.4.2;2.1.4.2. Nitric oxide binding to metmyoglobin;206
10.2.1.4.3;2.1.4.3. Nitric oxide binding to cytochrome c;208
10.2.1.4.4;2.1.4.4. Nitric oxide binding to Alcaligenes xylosoxidans cytochrome c;208
10.2.2;2.2. NO binding to iron(III) porphyrazine complexes;210
10.2.3;2.3. Nitrosylation reactions of iron(II) aqua and chelate complexes;213
10.2.3.1;2.3.1. Nitric oxide binding to the iron(II) center in ILs;215
10.2.3.2;2.3.2. Influence of the fluoride anion on autoxidation of [FeII(edta)(H2O)]2-;216
10.2.4;2.4. Reactivity of nitric oxide toward [Fe–S] models;218
10.2.5;2.5. Interactions of nitric oxide with pentacyanoferrate(II)/(III);221
10.2.5.1;2.5.1. Interaction of nitric oxide with pentacyanoferrate(III);221
10.2.5.2;2.5.2. Interaction of nitric oxide with pentacyanoferrate(II);223
10.3;3. Nitric Oxide Activation by Ruthenium(III) Centers;225
10.3.1;3.1. Nitric oxide binding to the RuIII(edta) complex;225
10.3.1.1;3.1.1. Interaction of RuIII(edta) with nitric oxide in buffered aqueous solution;226
10.3.1.2;3.1.2. Interaction of RuIII(edta) with nitric oxide in ILs;227
10.3.2;3.2. Interaction of nitric oxide with ruthenium(III) ammine and terpyridine complexes;228
10.3.2.1;3.2.1. Nitric oxide binding to ruthenium(III) ammine complexes;228
10.3.2.2;3.2.2. Nitric oxide binding to ruthenium(III) terpyridine complexes;230
10.3.3;3.3. Reactivity of NAMI-A complex toward nitric oxide;233
10.4;4. Reductive Nitrosylation Reactions;237
10.4.1;4.1. Reductive nitrosylation reactions of Fe(III) porphyrin complexes;237
10.4.2;4.2. Reductive nitrosylation of aquacobalamin and cobalt porphyrins;241
10.4.2.1;4.2.1. Reductive nitrosylation of water-soluble cobalt porphyrins;242
10.4.2.2;4.2.2. Reductive nitrosylation of aquacobalamin at low pH;245
10.5;5. Concluding Remarks;248
10.6;Acknowledgments;248
10.7;References;249
11;Chapter Five: New Insights on {FeNO}n (n=7, 8) Systems as Enzyme Models and HNO Donors;256
11.1;1. Background;257
11.2;2. {FeNO}7 Complexes as Models for Nonheme Oxygenase Enzymes;258
11.2.1;2.1. High-spin {FeNO}7 complexes;258
11.2.2;2.2. Low-spin {FeNO}7 complexes;263
11.3;3. {FeNO}7 Complexes as Precursors to {FeNO}8 Complexes;264
11.3.1;3.1. Low-spin {FeNO}8 complexes;264
11.3.2;3.2. High-spin {FeNO}8 complexes;268
11.4;4. Diiron Complexes Containing {FeNO}7 Unit(s);270
11.5;5. Summary and Outlook;273
11.6;References;275
12;Chapter Six: Design, Reactivity, and Biological Activity of Ruthenium Nitrosyl Complexes;278
12.1;1. Introduction;279
12.2;2. Tetraaza Ruthenium Complexes;281
12.3;3. Polypyridine Ruthenium Complexes as NO Delivery Systems;282
12.4;4. UV-Vis Electronic Spectrum;285
12.5;5. Electrochemistry;288
12.6;6. FTIR;290
12.6.1;6.1. Hydroxide electrophylic attack on bipyridine nitrosyl ruthenium complexes;290
12.7;7. Photochemical Reactivity;292
12.8;8. Vasorelaxation;295
12.9;9. Cytotoxicity;300
12.10;10. Neglected Tropical Diseases;302
12.11;11. Trinuclear Oxo-Centered Ruthenium Carboxylates;303
12.12;References;305
13;Chapter Seven: Complete and Partial Electron Transfer Involving Coordinated NOx;308
13.1;1. Introduction and Presentation of NOx Oxidation States;308
13.1.1;1.1. x=1+;309
13.1.2;1.2. x=0;309
13.1.3;1.3. x=1-;310
13.1.4;1.4. x=2-;311
13.2;2. Nitrosylmetal Complexes Without Additional Redox-Active Ligands;312
13.3;3. Nitrosylmetal Complexes with Additional Redox-Active Ligands;313
13.3.1;3.1. 1,4-Diaza-1,3-butadiene complexes;313
13.3.2;3.2. Porphyrin complexes;313
13.3.3;3.3. 1,2-Dioxolene complexes;316
13.4;4. Noninnocent Ligand Potential of the NO2-/NO2 Redox System;321
13.5;5. Conclusions;322
13.6;Acknowledgments;323
13.7;References;324
14;Chapter Eight: Oxidation Mechanism of Hydroxamic Acids Forming HNO and NO: Implications for Biological Activity;328
14.1;1. Introduction;329
14.2;2. HXs Oxidation In Vitro and In Vivo;330
14.2.1;2.1. Radiation studies;331
14.2.1.1;2.1.1. Pulse radiolysis;331
14.2.1.2;2.1.2. Steady-state radiolysis;334
14.2.1.3;2.1.3. Oxidation mechanism;335
14.2.2;2.2. Metmyoglobin and H2O2 reactions system;337
14.2.3;2.3. Effects of HXs on cells subjected to oxidative stress;340
14.2.4;2.4. SAHA as a radiosensitizer of hypoxic tumor cells;342
14.3;3. Conclusions;343
14.4;Acknowledgment;344
14.5;References;344
15;Chapter Nine: Reaction Steps in Nitrogen Monoxide Autoxidation;348
15.1;1. History;348
15.2;2. Gas-Phase Reaction and Atmospheric Chemistry;350
15.3;3. Liquid-Phase Reaction and Biology;351
15.4;4. Thermochemistry and Kinetics;352
15.5;5. Mechanisms;354
15.5.1;5.1. Termolecular Reaction;354
15.5.2;5.2. Steady-state Approach;354
15.6;6. Conclusions;365
15.7;Acknowledgments;365
15.8;References;366
16;Index;368
17;Contents of Previous Volumes;378

Leseproben

Chapter One NOx Linkage Isomerization in Metal Complexes
Dennis Awasabisah; George B. Richter-Addo    Department of Chemistry and Biochemistry, Stephenson Life Sciences Research Center, University of Oklahoma, Norman, Oklahoma, USA Abstract
The binding of small molecules to metals often imparts varied chemistry to the small molecules. Such chemistry is dependent on the coordination mode of the small molecule ligands, as the coordination mode affects the electronic distributions along the ligand atoms. In this review, we outline the current knowledge of the linkage isomerization of NOx ligands in their metal complexes for both non-porphyrin and porphyrin systems. We present their modes of preparation and detection and speculate on the consequences of such linkage isomerization on the resultant chemistry. Keywords Heme Hyponitrite Isomerization Isonitrosyl Linkage Nitrate Nitric oxide Nitrite Nitrosyl Porphyrin 1 Introduction
The interactions of ambidentate ligands with transitions metals have often resulted in complexes with very interesting chemistry. For example, the complex [(NH3)5Co(NO2)]Cl2, first prepared by Jörgensen (1) in 1894, contains the ambidentate ligand NO2 and the complex exists in two forms. Crystalline solids obtained for this compound showed a mixture of two different colored species: yellow and red, which were readily isolated with a pair of tweezers (1). Later, Werner identified these two species as isomers arising from the different modes of binding of the NO2 ligand to Co, either via the O or via the N atoms. This resulted in the birth of the concept of linkage isomerization in 1907 (2). About five decades later, Penland provided infrared spectroscopic data to show that the yellow [(NH3)5Co(NO2)]Cl2 complex had NO2 bound to Co via its N atom, and the red isomer had NO2 bonded to Co via the O atom (3). By way of definition, linkage isomerization may be defined as the existence of two or more species that have the same molecular formula, and the same bonding ligands, but differ in the mode of attachment of at least one of the ligands (usually ambidentate) to the central metal atom. Linkage isomerization in complexes containing several other ambidentate ligands including those of SCN-, SeCN-, CN-(4–6), and NO (5,7) have been reported. We wish to limit this review to linkage isomerization in NOx complexes and to provide current knowledge in the area of linkage isomerization partly because of the myriad of applications and relevance of NOx complexes. There are only a handful of recent reviews in the literature on linkage isomerization in NOx complexes, including a review by Coppens and Novozhilova on photoinduced isomerization (7), and a more recent forum paper on NOx linkage isomerization in porphyrin complexes (8). This review covers linkage isomerization deriving from isolable metal complex precursors. Thus, we will not cover the systems involving laser ablated atomic systems (9). The importance of linkage isomerization has been highlighted in a number of reviews (8,10,11). A good understanding of the various modes of binding of an ambidentate ligand, and factors that influence these modes of binding will provide more insight in the kind of chemistry they present. For instance, nitric oxide (NO) is known to bind to the iron center of a heme enzyme to carry out its function as a hypotensive agent (12–14). An increased knowledge of Fe–NO coordination has helped in designing better NO-releasing drugs, and understanding their use in the treatment of hypertension as in the case of sodium nitroprusside (SNP) (15,16). Recently, a book chapter was dedicated to a review on medical applications of solid NO complexes (17). Also, the chemistry of NOx complexes is relevant in understanding the mechanism of the denitrification process that forms part of the global nitrogen cycle (18–21), and in understanding the action of the metal-dependent reduction of nitrite (22). NOx species are generated by combustion processes in industries and automobiles, and may be produced naturally by lightning strikes. This has led to a rising interest in finding improved catalysts for removal of these toxic gases from the atmosphere (23–25). In addition, and more recently, metastable linkage isomers of NOx complexes have been generated to produce photoswitchable complexes which may be applied in ultrafast optical switching and storage devices (26–31). Recent work by Schuy (32), Cervellino (33), and Tahri (34) have shown how the nitroprusside anion [(CN)5Fe(NO)]2 - could be incorporated into silica gel pores to generate its corresponding linkage isomer for potential use in optical devices. Photoinduced linkage isomerism, Schaniel et al. have noted, is known to modify the polarizability of [(CN)5Fe(NO)]2 - so as to cause a macroscopic change of single-crystal refractive index according to the Lorentz–Lorenz equation (27). 1.1 Modes of binding of NOx moieties in monometallic complexes
1.1.1 Nitric oxide complexes NO is a colorless monomeric gas which is biosynthesized by the enzyme nitric oxide synthase (NOS) (35). NO is known to bind to transition metals in three main ways. The first is via the N end of the molecule to form the linear (Figure 1 Ia) and bent (Figure 1 Ib) nitrosyl (?1-NO) modes, or via the O end to produce the isonitrosyl (?1-ON) linkage isomer (Figure 1 Ic) (36). Isonitrosyl complexes of SNP (37), and some ruthenium nitrosyl complexes were detected in the solid state as metastable species just less than two decades ago by Coppens and coworkers (38). The third mode of binding is the side-on NO (or the ?2-NO) binding mode to a metal as shown in Figure 1 Id. Complexes containing this mode of binding were first demonstrated by Coppens and coworkers for their metastable SNP species (37). Side-on NO species were obtained as short-lived species from photolysis of (OEP)Ru(NO)(O-i-C5H11) and (OEP)Ru(NO)(SCH2CF3) porphyrin complexes (39). Theoretical evidence for the existence of the metastable modes of binding have been demonstrated for SNP (40–42) and for some (por)Fe(NO) models (43). Figure 1 Modes of binding of NOx moieties in monometallic complexes. 1.1.2 NO2 complexes The binding modes of NO2 have been reviewed by Hitchman and Rowbottom (44). Relevant to us in this review are the three nitrite binding modes shown in Figure 1 IIa–c. These are the N-nitro, O-nitrito, and the O,O-bidentate modes. The N-nitro mode has the nitrite ligand bound to the metal via the N atom (Figure 1 IIa). This appears to be the most common binding mode of NO2 in its complexes, thus this binding mode is usually referred to as the ground state binding mode for nitrite, although clearly this is an oversimplification. In the nitrito binding mode, NO2 is bound to the metal via the O atom as shown in Figure 1 IIb. Finally, in the O,O-binding mode, both oxygen atoms of nitrite are bound to the same metal to give an ?2-NO2 configuration as shown in Figure 1 IIc. 1.1.3 NO3 complexes There are two common binding modes of the nitrate 3- ligand. The first is binding via one oxygen atom to give the O-nitrato form (Figure 1 IIIa) and the second is binding through two NO3 oxygens to give the O,O-bidentate configuration (Figure 1 IIIb). The monodentate mode of binding has been observed in some metalloporphyrin complexes including (OEP)Fe(NO3) (45), (F8TPP)Fe(NO3) (46), (TpivPP)Fe(NO3)-(47), and (TPP)Mn(NO3) (48). Some examples of the O,O-bidentate binding mode in NO3-coordinated metalloporphyrins include (TPP)Fe(NO3) (49,50) and (TpivPP)Fe(NO3) (51). A review article on the coordination chemistry of the nitrate ligand was published in 1971 by Addison and Garner (52). 1.2 Methods that induce linkage...