 | Fehlner T.P. Molecular clusters: a bridge to solid-state chemistry / Fehlner T.P., Halet J.-F., Saillard J.-Y. - Cambridge: Cambridge University Press, 2007. - xi, 378 p.: ill. - Ref.: p.369-370. - Ind.: p.371-378. - ISBN 0-521-85236-6
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Preface ...................................................... ix
1 Introduction .................................................. 1
1.1 Molecular orbitals without the nasty bits ................. 2
1.2 Three-center bonds ....................................... 18
1.3 An orbital explanation of electron-counting rules ........ 22
Problems ................................................. 29
Additional reading ....................................... 32
2 Main-group clusters: geometric and electronic structure ...... 33
2.1 Definition of a cluster .................................. 33
2.2 Three-connect clusters ................................... 34
2.3 Four-connect and higher clusters ......................... 39
2.4 The Wade-Mingos electron-counting rule ................... 42
2.5 Closed-cluster composition and structure ................. 43
2.6 Open nido-clusters ....................................... 45
2.7 Open arachno-clusters .................................... 48
2.8 The closo-, nido-, arachno-borane structural paradigm .... 51
2.9 Localized bonds in clusters .............................. 53
2.10 Clusters with nuclearity greater than 12 ................ 59
2.11 Ligand-free clusters .................................... 64
2.12 When the rules fail ..................................... 69
Problems ................................................ 79
Additional reading ...................................... 81
3 Transition-metal clusters: geometric and electronic
structure .................................................... 85
3.1 Three-connect clusters ................................... 85
3.2 Small four-connect metal-carbonyl clusters and
the 14n + 2 rule ......................................... 90
3.3 Variations characteristic of metal clusters .............. 96
3.4 Naked clusters .......................................... 120
3.5 High-nuclearity clusters with internal atoms ............ 122
3.6 Nanoscale particles ..................................... 129
Problems ................................................ 132
Additional reading ...................................... 135
4 Isolobal relationships between main-group and
transition-metal fragments. Connections to organometallic
chemistry ................................................... 139
4.1 Isolobal main-group and transition-metal fragments ...... 139
4.2 Metal variation with fixed ancillary-ligand set ......... 148
4.3 Metal-ligand complex vs. heteronuclear cluster .......... 150
4.4 p-Block-d-block metal complexes ......................... 152
4.5 Carborane analogs of cyclopentadienyl-metal complexes ... 155
Problems ................................................ 161
Additional reading ...................................... 163
5 Main-group-transition-metal clusters ........................ 165
5.1 Isolobal analogs of p-block and d-block clusters ........ 165
5.2 Rule-breakers ........................................... 178
Problems ................................................ 201
Additional reading ...................................... 203
6 Transition to the solid state ............................... 205
6.1 Cluster molecules with extended bonding networks ........ 205
6.2 Outline of the electronic-structure solution in
a one-dimensional world ................................. 210
6.3 Complex extended systems ................................ 236
6.4 From the bulk to surfaces and clusters .................. 246
Problems ................................................ 253
Additional reading ...................................... 255
7 From molecules to extended solids ........................... 257
7.1 From a single atom to an infinite solid: the example
of C .................................................... 258
7.2 B clusters in solids: connections with molecular
boranes ................................................. 282
7.3 Molecular transition-metal complexes in solids .......... 287
7.4 Molecular vs. solid-state condensed octahedral
transition-metal chalcogenide clusters: rule-breakers
again ................................................... 291
7.5 Cubic clusters in solids ................................ 296
Problems ................................................ 299
Additional reading ...................................... 301
8 Inter-conversion of clusters and solid-state materials ...... 303
8.1 Cluster precursors to new solid-state phases ............ 303
8.2 Solid-state phases to molecular clusters ................ 309
8.3 Clusters to materials ................................... 314
8.4 A final problem ......................................... 319
8.5 Conclusion .............................................. 321
Appendix: Fundamental concepts: a concise review .............. 323
A1.1 Elements ................................................. 324
A1.2 Atomic properties ........................................ 324
A1.3 Homoatomic substances .................................... 330
A1.4 Heteroatomic substances .................................. 337
Problem Answers ............................................... 349
Chapter 1 ................................................ 349
Chapter 2 ................................................ 352
Chapter 3 ................................................ 357
Chapter 4 ................................................ 360
Chapter 5 ................................................ 362
Chapter 6 ................................................ 363
Chapter 7 ................................................ 366
References .................................................... 369
Index ......................................................... 371
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