* Provides an authoritative, definitive review addressing all aspects of organometallic chemistry
* Useful to researchers within this active field and is a must for every modern library of chemistry
* High quality research book within this rapidly developing field
Almost all branches of chemistry and material science now interface with organometallic chemistry - the study of compounds containing carbon-metal bonds. This widely acclaimed serial contains authoritative reviews that address all aspects of organometallic chemistry, a field which has expanded enormously since the publication of Volume 1 in 1964.* Provides an authoritative, definitive review addressing all aspects of organometallic chemistry* Useful to researchers within this active field and is a must for every modern library of chemistry* High quality research book within this rapidly developing field
Cover 1
Advances in Organometallic Chemistry 4
Contents 6
Contributors 8
Metal Complexes of Monocarbon Carboranes: A Neglected Area of Study? 10
Introduction 10
Synthesis 12
Triruthenium and Triosmium Complexes 12
Mononuclear Compounds of Iron, Molybdenum, Tungsten, Rhenium, Platinum, Nickel and Cobalt 14
Reactions 16
Ruthenium and Osmium Cluster Compounds 16
Mononuclear Metal Compounds 18
Formation of Charge-Compensated Complexes with Donor Ligands 18
Complexes of Iron 18
Complexes of Molybdenum and Tungsten 21
Complexes of Nickel and Cobalt 25
Protonation and Related Reactions of Platinum Complexes 27
Zwitterionic Bimetallic Compounds† 31
Monocarbollide–Metal Complexes with Non-Icosahedral Core Frameworks 37
Chemistry of the 11-Vertex Dianions [1,1,1-(CO)3-2-Ph-closo-1,2-MCB9H9]2- (M = Mn, Re) 38
Chemistry of the 11-Vertex Trianions [1,3,6-{M(CO)3}-3,6-(µ-H)2-1,1,1-(CO)3-2-Ph-closo-1,2-MCB9H7]3- (M = Mo, W) 45
Acknowledgements 47
References 47
Synthesis of Novel Silicon-Containing Compounds via Lewis Acid-Catalyzed Reactions 50
Introduction 50
Allylsilylation Reactions with Allyltriorganosilanes 51
Allylsilylation of Alkenes 51
Allylsilylation of Linear Alkenes 52
Allylsilylation of 4-(Trimethylsilylmethyl)-1-Alkenes 52
Allylsilylation of Cycloalkenes 53
Allylsilylation of 1-Allyl-2-(Trimethylsilyl)Cycloalkenes 54
Allylsilylation of Diallylsilanes 55
Allylsilylation of Conjugated Dienes 55
Allylsilylation of Alkynes 57
Intramolecular Alkenyl-Migration Reaction of Alkenylchlorosilanes 58
Friedel–-Crafts Alkylation Reaction with Organosilicon Compounds 59
Alkylation with Allylchlorosilanes 59
Alkylation with Vinylchlorosilanes 62
Alkylation with (.-Chloroalkyl)chlorosilanes 64
Alkylation with (Polychloroalkyl)chlorosilanes 65
Hydrosilylation Reaction with Triorganosilanes 66
Acknowledgments 67
References 67
Bidentate Group 13 Lewis Acids with ortho-Phenylene and peri-Naphthalenediyl Backbones 70
Introduction 70
Synthesis 71
Boron Polydentate Lewis Acids 71
Ortho-Phenylene Boron Derivatives 71
1,8-Naphthalenediyl Boron Derivatives 75
Aluminum, Gallium and Indium Polydentate Lewis Acids 82
Ortho-Phenylene Aluminum, Gallium and Indium Derivatives 83
1,8-Naphthalenediyl Gallium and Indium Derivatives 89
Interaction with Lewis Basic Substrates 94
Complexation of Organic Substrates 94
Complexation of Organic Carbonyls 94
Complexation of Diazines 94
Complexation of Anions 98
1,8-Naphthalenediyl-diboranes 98
1,8-Naphthalenediyl Gallium Species 101
Ortho-Phenylene Diboranes and Dialanes 102
Conclusion 106
Acknowledgments 107
References 107
Metallasilsesquioxanes 110
Introduction 110
Silsesquioxane Precursors 114
Metallasilsesquioxanes 115
Metallasilsesquioxanes of Main-Group Metals 115
Group 1 Metal Derivatives (Li, Na, K): Useful Starting Materials 115
Group 2 Metal Derivatives (Be, Mg) 117
Group 13 Metal Derivatives (B, Al, Ga, In, Tl) 119
Group 14 Metal Derivatives (Ge, Sn) 127
Metallasilsesquioxanes of the Early Transition Metals 129
Group 3 Metal Derivatives (Sc, Y, La, and the Lanthanides and Actinides) 129
Group 4 Metal Derivatives (Ti, Zr, Hf) 134
Group 5 Metal Derivatives (V, Nb, Ta) 146
Metallasilsesquioxanes of the Middle and Late Transition Metals 149
Group 6 Metal Derivatives (Cr, Mo, W) 149
Group 7 Metal Derivatives 151
Group 8 Metal Derivatives (Fe, Ru, Os) 152
Group 9 Metal Derivatives (Co, Rh) 155
Group 10 Metal Derivatives (Pt) 156
Group 11 Metal Derivatives (Cu, Au) 157
Future Outlook 157
Acknowledgments 159
References 159
Cations of Group 14 Organometallics 164
Introduction 164
Synthetic Approaches to R3E+ Ions 165
Heterolytic Cleavage of E–X Bonds 165
Hydride Transfer Reaction 166
Electrophilic Cleavage of E-Alkyl and E-Silyl Bonds 168
Oxidative Cleavage of E– E and E–C Bonds 169
Addition of Electrophiles to Heavy Carbenes 173
Structure and Properties of R3E+ Cations 174
Theoretical Considerations 174
The EH3+ Potential Energy Surface 174
Thermodynamic Stability of R3E+ Cations 175
NMR Spectroscopic Properties of R3E+ Cations 178
29Si NMR Spectroscopic Data of Silylium Ions and Related Species 179
Si NMR Chemical Shift Calculation for Silylium Ions and Related Species 179
Experimental 29Si NMR Data for Silylium Ions and Related Species 181
29Si NMR Data for Silyl-Substituted Germylium and Stannylium Ions 188
119Sn NMR Spectroscopic Data of Stannylium Ions and Related Species 188
Sn NMR Chemical Shift Calculations for Stannylium Ions and Related Species 189
Experimental 119Sn NMR Data for Stannylium Ions and Related Species 190
207Pb NMR Spectroscopic Data of Plumbylium Ions and Related Species 195
13C NMR Spectroscopic Data of Organosubstituted R3E+ Cations 197
Miscellaneous Spectroscopic Data of R3E+ Cations 198
Solid State Structure of R3E+ Cations and Related Species 199
Solid State Structure of R3E+ Cations 199
Solid State Structure of Intramolecularly Stabilized R3E+ Cations 205
Solid State Structure of Cation/Anion Aggregates of R3E+ Cations 208
Solid State Structure of Cation/Solvent Complexes of R3E+ Cations 212
A chemistry of R3E+ cations 215
Acknowledgements 219
References 219
Recent Advances in Nonclassical Interligand Si…H Interactions 226
Introduction 226
Silane s-Complexes and Si–-H…M Agostic Complexes 228
Silane s-Complexes. A Short Historical Overview of Benchmark Results 228
Dewar– Chatt– Duncanson Scheme – A Simple Model for Electron-Deficient Three-Center Interactions 229
Structural Features of Silane s-Complexes 231
Spectroscopic Features of Silane s-Complexes 234
NMR Spectroscopy. The Saga of Silicon–Proton Coupling Constant 234
NMR Spectroscopy. The 1H NMR Spectra 238
IR Spectroscopy 238
Recent Results on Silane s-Complexes 238
Group 3 and 4 Metals 239
Group 5 Metals 243
Group 6 Metals 244
Group 7 Metals 245
Group 8 Metals 247
Groups 9–10 Metals 253
Group 11 Metals 256
Si…H…M Agostic Bonding 256
d- and Other High-Order Si…H…M Agostics 257
.-Agostic Si…H…M Interaction 258
ß-Agostic Si…H…M Interaction 260
Carbon Bridges 260
Phosphorus Bridge 267
Nitrogen Bridge 268
a-Agostic Si…H…M Interaction 274
Silylhydride Complexes with Interligand Hypervalent Interactions M–-H…Six 279
A Short Remark on the Heuristic Aspect 279
IHI MH…Six in Metallocene and Related Ligand Environments 281
IHI in Niobocene Complexes 281
Monosilyl and Symmetric bis(silyl) Derivatives 281
Asymmetric bis(Silyl) Niobocene Derivatives 286
The Dependence of IHI MH…EX on the Nature of Group 4 Element E 287
IHI in Titanocene Silylhydrides 290
IHI in Group 5 Cp-Imido Complexes 292
Cp/Imido Complexes of Tantalum with IHI 292
Silylhydride Derivatives of Niobium Supported by the Cp/Imido Ligand Set 295
The IHI MH…Six in Half-Sandwich Complexes of Ruthenium 296
ß-IHI 297
IHI MH…Six in Complexes not Isolobal with Metallocenes 298
Comparison of IHI with Residual s Interactions in Silane Complexes 299
Multicenter H…Si Interactions in Polyhydridesilyl Complexes 300
Evidence for Multicenter H…Si Interactions 300
Comparison of Multicenter H…Si Interactions with IHI and Residual s-Interactions in Silane Complexes 310
A Comment on the Terminology 310
Conclusions and Outlook 312
Acknowledgments 313
References 313
Index 320
Cumulative List of Contributors for Volumes 1–36 326
Cumulative Index for Volumes 37–53 330
Metal Complexes of Monocarbon Carboranes: A Neglected Area of Study?
Thomas D. McGratha; F. Gordon A. Stonea, * a Department of Chemistry and Biochemistry, Baylor University, Waco, TX 76798-7348, USA
* Corresponding author. email address: gordon_stone@baylor.edu
I INTRODUCTION
The first metallacarboranes were isolated in M. F. Hawthorne's laboratory and contained a metal ion, two carbon and nine boron atoms forming an icosahedral {closo-MC2B9} cage structure.1,2 It was immediately recognized that these species may be viewed as having metal ions coordinated in a pentahapto manner by the open face of a [nido-7,8-C2B9H11]2– dianion. This was a useful formalism since it emphasized an isolobal relationship between the carborane dianion and the ubiquitous [C5H5]– ligand. Following isolation of metal dicarbollides from reactions between metal salts and salts of [nido-7,8-C2B9H11]2–, it was logical that the monocarbon trianion [nido-7-CB10H11]3– would react in a similar way to afford monocarbon metallacarboranes also with icosahedral frameworks. Indeed, a few complexes of this kind were isolated3 soon after the first dicarbon analogues were discovered. Importantly in the early work, two types of monocarbollide metal compound were characterized. In the first a metal ion is sandwiched between [nido-7-CB10H11]3– ligands, as in the FeIII complex [commo-2,2′-Fe-(closo-2,1-FeCB10H11)2]3– (1) (Chart 1). In the second the cage-carbon atom carries an NR3 or an NR2 group, with the metal ion sandwiched between [7-NR3-nido-7-CB10H10]2– groups, as in the FeIII complex [commo-2,2′-Fe-(1-NH3-closo-2,1-FeCB10H10)2]– (2), or [7-NR2-nido-7-CB10H10]3– groups as in [commo-2,2′-Ni-(1-NH2-closo-2,1-NiCB10H10)2]2– (3). The zwitterionic ligands [7-NR3-nido-7-CB10H10]2– are isolobal with the dicarbollide anion [nido-7,8-C2B9H11]2–, whereas the trianions [7-NR2-nido-7-CB10H10]3– are isolobal with [nido-7-CB10H11]3–.
Chart 1
In what has become a very large field of study during the past 40 years, metallacarborane chemistry has primarily focused on species with cages containing two or more carbon atoms,4,5 whereas monocarbollide metal complexes have received very little attention.4,6,7 The neglect of this area is somewhat surprising because monocarbollide metal complexes having [nido-7-CB10H11]3–, [7-NR3-nido-7-CB10H10]2–, or [7-NR2-nido-7-CB10H10]3– groups would be expected to display reactivity patterns different from those of the corresponding dicarbollide species. In particular, the higher formal negative charge associated with the trianions [nido-7-CB10H11]3– and [7-NR2-nido-7-CB10H10]3–, compared with the dianion [nido-7,8-C2B9H11]2–, renders metal complexes of the trianions more reactive towards electrophiles. As will be described later this feature provides avenues for introducing functional groups into a carborane cage, a topic of growing interest.
In metallacarborane chemistry it can be argued that it is more profitable to study molecules having half-sandwich ‘piano-stool’ structures than those with ‘full-sandwich’ structures. This is because in the piano-stool complexes the metal is ligated on one side by the carborane cage systems [{7,8-R2-nido-7,8-C2B9H9} (R=H or Me), {nido-7-CB10H11}, {7-NR2-nido-7-CB10H10}, or {7-NR3-nido-7-CB10H10}] and on the other side by the conventional ligands (CO, PR3, CNR, alkynes, etc.) of coordination chemistry. With a combination of different coordinated groups within the coordination sphere of the metal there is the probability of reactions occurring between the ligands and other substrate molecules, and also with the carborane cage itself, with the latter thus adopting a non-spectator role in the chemistry derived.8 Both mono- and di-carbollide metal carbonyl half-sandwich complexes are especially desirable as synthons. They have isolobal relationships with cyclopentadienide metal carbonyls that are known to function as precursors to numerous other species through the lability of their carbonyl groups. Dicarbollide metal carbonyls display a very extensive chemistry, as shown by [3,3,3-(CO)3-closo-3,1,2-RuC2B9H11] (4),9 thereby pointing to the desirability of obtaining related monocarbollide metal carbonyl species for use in synthesis (Chart 2).
Chart 2
In an attempt to redress the imbalance between studies on the dicarbollide and monocarbollide metal compounds we began a comprehensive study of the latter, concentrating our studies on the piano-stool-type complexes for the reasons given above. Our progress to date in this area will be the subject of this review. So far, most of the work has involved compounds in which the metal is one of the 12 vertexes in a {closo-2,1-MCB10} cage system, thereby complementing the host of studies made on their {closo-3,1,2-MC2B9} counterparts. However, as will also be described, preliminary investigation of 11-vertex {closo-1,2-MCB9} systems is revealing the existence of unprecedented molecular structures in the metallacarborane field. We do not review in this chapter recent developments in the chemistry of monocarbollide–metal complexes in which the cage-carbon carries an NR3 or NR2 group because we have recently given an account of such species.10
II SYNTHESIS
A Triruthenium and Triosmium Complexes
The methodologies used to prepare monocarbollide metal carbonyls resemble those used to obtain cyclopentadienide metal carbonyls. The latter are generally obtained by one of two methods: heating cyclopentadiene or a substituted cyclopentadiene with a metal carbonyl or a metal carbonyl anion, or treating the carbonyl or a halo derivative of it with a salt of the cyclopentadienide ion. Similarly, procedures involving either heating a nido-carborane with a metal carbonyl or treating a metal carbonyl or a carbonyl-metal halide with the salt obtained by deprotonating a nido-carborane have afforded monocarbollide metal carbonyl complexes.
Thus, in tetrahydrofuran (THF) at reflux temperatures [Ru3(CO)12] and [NHMe3][nido-7-CB10H13] react to give an anionic trinuclear ruthenium complex [PPh4][2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H9] (5)* (Chart 3) following the addition of [PPh4]Cl.11 Subsequent analysis of this system revealed evidence for traces of the mononuclear species [NHMe3][2,2,2-(CO)3-closo-2,1-RuCB10H11] (6) in the initial product mixture, but its isolation in a pure form proved impossible.12 In contrast, the corresponding reaction between [Os3(CO)12] and [N(PPh3)2][nido-7-CB10H13] in refluxing bromobenzene affords an approximately equimolar mixture of the analogous triosmium cluster [N(PPh3)2][2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Os2(CO)6}-closo-2,1-OsCB10H9] (7) and the monoosmium complex [N(PPh3)2][2,2,2-(CO)3-closo-2,1-OsCB10H11] (8).12 The structures of the anions of 5 and 7 are similar to that of neutral [3,3-(CO)2-1,2-Me2-4,8-(μ-H)2-3,4,8-{Ru2(CO)6}-closo-3,1,2-RuC2B9H7] (9) obtained from the reaction between [Ru3(CO)12] and 7,8-Me2-nido-7,8-C2B9H11.13 In all the trimetal species a {nido-CB10} or {nido-C2B9} framework bridges a triangular arrangement of ruthenium or osmium atoms with the open or faces, respectively, coordinated in a pentahapto fashion to one metal atom while the carborane cage forms two exo-polyhedral B–HM bonds with the other two metal atoms.
Chart 3
Surprisingly, instead of affording a mixture containing the anions of the cluster compound 7 and the mononuclear species 8, the complex [12-NMe3-2,2,2-(CO)3-closo-2,1-OsCB10H10] (10) is obtained by heating [Os3(CO)12] with [NHMe3][nido-7-CB10H13] in refluxing bromobenzene. The NMe3 group is attached to a boron atom in the pentagonal belt lying above that of the ring 5-coordinated to the metal.12 The source of the trimethylamine group must be the cation [NHMe3]+, but the pathway by which its NMe3 fragment migrates to the cage is not clear.
B Mononuclear Compounds of Iron, Molybdenum, Tungsten, Rhenium, Platinum, Nickel and Cobalt
Reactions between salts of [nido-7-CB10H13]– and [Fe3(CO)12] afford the mononuclear anionic iron compound [2,2,2-(CO)3-closo-2,1-FeCB10H11]–, typically isolated as its [N(PPh3)2]+ salt (11) (Chart 4).14 No anionic triiron complex analogous to 5 and 7 is formed in this reaction. The anionic mononuclear iron, ruthenium and osmium complexes and the previously mentioned neutral mononuclear ruthenium dicarbollide complex 4, obtained from [Ru3(CO)12] and...
Erscheint lt. Verlag | 9.1.2006 |
---|---|
Sprache | englisch |
Themenwelt | Sachbuch/Ratgeber |
Naturwissenschaften ► Chemie ► Anorganische Chemie | |
Naturwissenschaften ► Chemie ► Organische Chemie | |
Technik | |
ISBN-10 | 0-08-045814-9 / 0080458149 |
ISBN-13 | 978-0-08-045814-4 / 9780080458144 |
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