List of Posters and Contributed Oral Presentations

Posters

G. J. M. Gruter, B. L. M. van Baar, M. Hogenbirk, O. S. Akkerman, and F. Bickelhaupt An Interface for the Introduction of Air and Moisture Sensltive Compounds into a Magnetic Sector Mass Spectrometer

J. P. Leal, N. Marques, A. Pires de Matos, A. M. Galvao, M. J. Calhorda, and J. A. Martinho Simoes Uranium-Ligand Bond Dissociation Enthalpies

N. Papadopoulos, C. Hasiotis, G. Kokkinidis, and G. Papanastasiou Determination of Kinetic Parameters of an Homogeneous Chemical Reaction Following an Electrochemical Reaction, Using 3D Electrochemistry

J. S. Chickos, D. G. Hesse, and J. F. Liebman Estimation of the Heat Capacities of Solid and Liquid Organic Compounds

L. S. Sunderlin, D. Wang, and R. R. Squires Metal Carbonyl Anion Bond Strengths

M. Tilset and A. Pedersen Chemical and Electrochemical Oxidation of CpCo(PPh3)Me2

B. Salih and N. Balcioglu Energetics of Mass Spectral Isomerization of 1,5-cyclodecadiene

J. Catalan and J. C. del Valle Experimental Acidity of Carbazole

S. T. Kapellos, A. Mavridis, and J. F. Harrison Electrostatic, High Spin Bonding in MNH~ (M=Sc, Ti, V, Cr. and Mn)

J. Mar9alo and A. Pire3 de Matoso D(XnM-L)ID(H-L) and ~Hf(XnML)/~Hf(HL) Correlations in Organolanthanide. Actinide, and Early Transition Metal Compounds

D. Clemmer and P Armentrout + + +

Understanding M -NH2, M -OH. and M -NO Bond Energies: Covalent and Dative Interactions

M. Azzaro, S. Breton, M. Decouzon, S. Geribal~i + FT-[CR Study of Gas-Phase Reactions of Sc , Y , and Lu with Silane and Alkoxysilanes

H. J. Arnold, J. P. Fitzgerald, and J. P. Collman Heterometallic Metal-Metal Bonded Dimers

424

A. R. Dias, H. P. Diogo, M. E. Minas da Piedade, J. A. Simoni, and J. A. Martinho Simoes Energetics of Zr-H, Zr-C, Zr-I, and Zr-OR Bonds in the Complexes Zr(Cp)2(Cl)L

P. Dias, A. R. Dias, J. A. Simoni, C. Teixeira, and J. A. Martinho Simoes Photocalorimetry. A Microcalorimetric System for Probing the Energetics of Light-Induced Reactions in Solution

H. Alt, P. Dias, A. R. Dias, R. Santos, and J. A. Martinho Simoes Energetics of Titanium-Phosphorus Bonds in the Complexes Ti(Cp)2(CO)(PR3) (R=Me, Et) and Ti(Cp)2(PMe3)2

T. Burkey New Results on an Old Photochemical Reaction

Oral Presentations

J. S. Chickos, D. G. Hesse, and J. F. Liebman Estimations of Sublimation Enthalpies

G. J. M. Gruter, B. L. M. van Baar, M. Hogenbirk, O. S. Akkerman, and F. Bickelhaupt An Interface for the Introduction of Air and Moisture Sensitive Compounds into a Magnetic Sector Mass Spectrometer

S. T. Kapellos, A. Mavridis, and J. F. Harrison Low Spin Bonding in MNH2 (M=Sc, Ti, V, Cr, and Mn)

C. G. Screttas and M. Micha-Screttas Correlating Spectroscopic Electronegativities with Thermochemical Data

M. Azzaro, S. Breton, M. Decouzon, S. Geribal~i + FT-ICR Study of Gas-Phase Reactions of Sc , Y , and Lu with Silane and Alkoxysilanes

H. J. Arnold, J. P. Fitzgerald, and J. P. Collman Heterometallic Metal-Metal Bonded Dimers

B. Wayland Thermochemistry of Rhodium Dimers

A. S. Miller Acidities of Metal Hydrides

List of Participants

Jorge M. M. Abalroado Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Peter B. Armentrout Department of Chemistry, University of Utah, Salt Lake City, Utah 8411, U.S.A.

Hilary J. Arnold Department of Chemistry, Stanford University, Stanford, California 94305, U.S.A.

Murat Azik Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, Turkey

Jack L. Beauchamp Noyes Laboratory, California Institute of Technology, Pasadena, California 91125, U.S.A.

Margareta R. A. Blomberg Institute of Theoretical Physics, University of Stockholm, Vanadisvagen, S-11346 Stockholm, Sweden

Sylvie Breton Laboratoire de Chimie Physique Organique, Universite de Nice-Sophia Antipolis, Parc Valrose, 06034 Nice Cedex, France

Theodore J. Burkey Department of Chemistry, Memphis State University, Memphis, Tennessee 38152, U.S.A.

Maria J. Calhorda Centro de Tecnologia Quimica e Biol6gica, Rua da Quinta Grande, 6, Apartado 127, Oeiras, Portugal

Teresa Canada Instituto de Quimica Fisica Rocasolano, CSIC, Calle Serrano 119, E-28006 Madrid, Spain

Alexander S. Carson Department of Physical Chemistry, The University of Leeds, Leeds LS2 9JT, U.K.

James S. Chickos Department of Chemistry, College of Arts and Sciences, University of Missouri-St. Louis, 8001 Natural Bridge Rd., St. Louis, Missouri 63121-4499, U.S.A.

425

David E. Clemmer Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, U.S.A.

Joseph A. Connor Chemical Laboratory, The University, Canterbury, Kent CT2 7NH, U.K.

Alberto Romao Dias Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Palmira B. Dias Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Herminio P. Diogo Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Maria Teresa Leal da Silva Duarte Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Ender Erdik Department of Chemistry, Ankara University, Ankara, Turkey

Eduardo Peris Fajarnes Departament de Quimica Inorganica, Universitat de Valencia, Doctor Moliner 50, 46100 Burjassot, Valencia, Spain

Adelino M. Galvao Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Ayten G09men Department of Chemistry, Istanbul Technical University, I.T.O. Fen-Ed. Fak. Kimya Bal., Maslak, 80626 Instanbul, Turkey

Jorge M. Gon9alves Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Pra9a Gomes Teixeira, 4000 Porto, Portugal

Gert-Jan Gruter Scheikundig Laboratorium, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands

William D. Jones Department of Chemistry, University of Rochester, Rochester, New York 14627, U.S.A.

George Kalatzis Inorganic Chemistry Laboratory, Department of Chemistry, University of Athens, Panepistimiopolis, Kouponia, 157 01 Athens, Greece

S. T. Kapellos Physical Chemistry Laboratory, Department of Chemistry, University of Athens, Panepistimiopolis, Kouponia, 157 71 Athens, Greece

Onel Koklli Department of Chemistry, Istanbul Technical University, Fen-Ed. Fak. Kimya Bal., Maslak, 80626 Instanbul, Turkey

Juan C. del Valle Lazaro Departamento de Qui~ica Fisica Aplicada, C II. 203, Universidad Autonoma de Madrid, E-28049 Madrid, Spain

Joao Paulo Leal Departamento de Quimica, Laborat6rio Nacional de Engenharia e Tecnologia Industrial, 2686 Sacavem Codex, Portugal

Joaquim Mar~alo Departamento de Quimica, Laborat6rio Nacional de Engenharia e Tecnologia Industrial, 2686 Sacavem Codex, Portugal

Tobin J. Marks Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60201, U.S.A.

Ant6nio Pires de Matos Departamento de Quimica, Laborat6rio Nacional de Engenharia e Tecnologia Industrial, 2686 Sacavem Codex, Portugal

M. Agostinha R. Matos Departamento de Quimica, Faculdade de Ci~ncias da Universidade do Porto, Pra~a Gomes Teixeira, 4000 Porto, Portugal

Amy E. Stevens Miller PL/LID, 1102F Greiner St .. Hanscom AFB, MA 01731-5000, U.S.A.

Manuel Joao Monte Departamento de Quimica, Faculdade de Ci~ncias da Universidade do Porto, Pra~a Gomes Teixeira, 4000 Porto, Portugal

Peter Mulder Center for Chemistry and the Environment, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, The Netherlands

Helena I. Seguro Nogueira

427

Departamento de Quimica, Universidade de Aveiro, 3800 Aveir'o, Portugal

Rafael Notario Instituto de Quimica Fisica Rocasolano, CSIC, Calle Serrano 119, E-28006 Madrid, Spain

Nikos Papadopoulos Laboratory of Physical Chemistry, Department of Chemistry, University of Thessaloniki, Thessaloniki 54006, Greece

428

Astrid Pedersen Department of Chemistry, University of Oslo, P. O. Box 1033, Blindern, N-0315 Oslo 3, Norway

Maria Angeles Ubeda Picot Departament de Quimica Inorganica, Universitat de Valencia, Doctor Moliner 50, 46100 Burjassot, Valencia, Spain

Manuel E. Minas da Piedade Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Geoffrey Pilcher Department of Chemistry, University of Manchester, Manchester M13 9PL, U.K.

David E. Richardson Department of Chemistry, University of Florida, Gainesville, Florida 32611, U.S.A.

Bekir Salih Department of Chemistry, Faculty of Engineering, Hacettepe University, Beytepe Campus, 06532 Ankara, Turkey

Luis M. N. B. F. Santos Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Pra9a Gomes Teixeira, 4000 Porto, Portugal

Rui M. Borges dos Santos Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

C. G. Screttas National Hellenic Research Foundation, 48 Vassileos Constantinov Av., Athens 116 35, Greece

Manuel A. V. Ribeiro da Silva Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Pra9a Gomes Teixeira, 4000 Porto, Portugal

Maria das Dores Ribeiro da Silva Departamento de Quimica, Faculdade de Ciencias da Universidade do Porto, Pra9a Gomes Teixeira, 4000 Porto, Portugal

Jose A. Martinho Simoes Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Jose de Alencar Simoni Instituto de Quimica, Universidade Estadual de Campinas, 13081 Campinas, S. Paulo, Brazil

Henry A. Skinner Department of Chemistry, University of Manchester, Manchester M13 9PL, U.K.

Robert R. Squires Department of Chemistry, Purdue University, West Lafayette, Indiana 47906, U.S.A.

Lee S. Sunderlin Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, U.S.A.

Clementina Teixeira Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Mats Tilset Department of Chemistry, University of Oslo, P. O. Box 1033, Blindern, N-0315 Oslo 3, Norway

Tito da Silva Trindade

429

Departamento de Quimica, Universidade de Aveiro, 3800 Aveiro, Portugal

Chris Tsiamis Department of General and Inorganic Chemistry, Aristotelian University, Thessaloniki 54008, Greece

Canan Vnaleroglu Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, Turkey

Luis Filipe Coelho Veiros Departamento de Engenharia Quimica, Instituto Superior Tecnico, 1096 Lisboa Codex, Portugal

Robin Walsh Department of Chemistry, University of Reading, Whiteknights, P.O. Box 224, Reading RG6 2AD, U.K.

Bradford B. Wayland Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, U.S.A.

Danial D. M. Wayner Division of Chemistry, National Research Council, 100 Sussex Drive, Ottawa, Ontario KIA OR6, Canada

Tom Ziegler Department of Chemistry, University of Calgary, Calgary, Alberta T2N 1N4, Canada

Subject Index

Ab initio 299-301, 324, 329, 331, 357, 358, 362, 363, 365-377, 387-418

Acidity 253-266 solvation effects 263-266 substituent effects 259, 260-266

Actinometry 87 Agostic bond (see also Metal-alkane ~ complexes and Metal-silane ~

complexes) 84, 90, 331, 378, 406 Alkane dehydrogenation 303, 304 Aluminium compounds 14, 15 Antimony compounds 4, 21, 22 ~2-Arene coordination 55-63 Arsenic compounds 4, 21, 22, 29

Backbonding 83, 86 Bismuth compounds 4, 21, 22, 29 Bond dissociation enthalpy

absolute values in solution 36 anchor 36, 199-201 C-H in alkanes 174-176 Co-C in co-enzyme B12 318, 319 Co-CH 193 Co-CH(Me)Ph 217 Co-CH2Ph 211-213 CO+-CH4 347, 349 Co+-C2H4 311, 350 Co+-C2H6 341, 349 Co+-C3H6 309-311, 350 Co+-C3H8 349 Co + -co 311 Co--CO 279, 281 Co-H 123, 260, 281, 329, 367 Co + -H20 346 Co+-ligand :111 Co-Me 367 Co-Mn 191 Co-He 191 Cr-alkane 80-82, 85, 86, 91, 92 Cr-a~ine 82, 83 Cr-arene 48, 91, 92, 200 Cr-CO 80, 81, 85, 86, 190, 279, 366 Cr + -CO 342, 345 Cr--CO 279, 281, 283 Cr-cy-C6H12 91 Cr-dichloroethane 91, 92 Cr-H 123 Cr+-H20 346 Cr-hexene 91 Cr-1 igand 2.43

431

432

Cr-silane 85, 86 Cr-tetrachloromethane 91 Cu + -H20 346 Cu-ligand 141, 143 definition 131-133 electronegativity effect 37, 217-220 electronic effect 210-217, 329, 331 enthalpy of reaction 199 f-element-ligand 14, 36-39, 43, 48, 49, 367 Fe-C 193 Fe+-CH4 347-349 Fe+-C2H4 311, 350 Fe+-C2H6 349 Fe-C3Hs 192 Fe+-C3H6 311, 350, 351 Fe+-C3H8 349, 351 Fe-CO 190, 193, 279, 280, 282 Fe+-CO 311, 342-344, 348 Fe--CO 278-280 Fe-Fe 193 Fe-H 123, 245 Fe+-H20 346, 348 Fe-ligand 243, 245, 311 Fe-olefin 192, 283 Fe-S 194 fragments M(CH4)~ 347-349 fragments M(CO)~ 342-345, 348 fragments M(CO)~ 278-282 fragments M(H20)~ 345-348 fragments ML and ML+ 294, 299-301, 311, 325-341, 349-351 fragments ML~ 311, 339, 341, 349 Ge-C 149-151 Ge-Ge 150 Ge-H 209 Ge-O 150, 151 heterolytic 96, 241, 243, 244 Hf-arene 48 Hf-H 367 Hf -ligand 244 Hf-Me 367 Hg-C 145, 146 internal rotation barrier 209 Ir-H 329, 367 Ir-Me 367 La-Cp 14 mean 3-7, 13, 14, 21, 201, 203, 204, 207 mean in cations and neutrals 242-244 Mn-alkane 85, 86 Mn-alkyl 203, 207, 208, 366, 367 Mn-benzyl 192, 203 Mn-CO 85, 86 Mn+-CO 314-316, 342, 345

Mn--co 279, 281 Mn-C3Hs 192 Mn-H 123, 260, 261, 367 Mn+-H20 346 Mn-ligand 243 Mn-Mn 191 Mn-Re 191, 192 Mn-silane 85, 86 Mo-alkane 80-82, 85, 86 Mo-alkyl 203 Mo-arene 48 MO-C2H4 413-416 Mo-CO 81, 82, 85, 86, 190, 366 Mo-H 123, 144 Mo-ligand 243 Mo-Mo 204, 205 Mo-O 204, 205 Mo-silane 85, 86 Nb-C2H4 413-416 Nb-O 21 Nd-X 38 Ni-CO 190, 279, 366, 416-418 Ni--CO 279, 281, 283 Ni+-CO 342, 345 Ni-H 245 Ni+-H20 346 Ni-ligand 243, 245 Pd-C2H4 413-416 Pt-ligand 227, 228 radical cations 99-103 Re-H 123, 261, 367 Re-Me 207, 208, 367 Rh-C 69-73 Rh-CHO 70, 71, 73 Rh-CH2(OH)Bu 71, 73 Rh-CH2Ph 72, 73 Rh-C2H4 413-416 Rh-Et 72, 73 Rh-H 69-71, 301, 367 Rh-Me 71, 73, 301, 367 Rh-Ph 54 Rh-Pr 54 Rh-Rh 69, 70 RU-C2H4 413-416 Ru-H 123, 245 Ru-ligand 227, 228, 245 Sc-Cp 14 Si-C 177 Si-H 172, 175-177, 208 Si-Si 172,177,178 Sm-X 37-39 Sn-C 146-148, 151, 152

433

434

Sn-O 148, 151 Sn-Sn 146, 148 stepwise 3, 6, 146, 341, 342-349, 416-418 sterie effect 82, 83, 144, 210-216, 329, 331 stretching frequency 206-209 Ta-O 21 TC-C2H4 413-4J6 Tc-H 367 Tc-Me 367 Th-H 367 Th-Me 367 Th-X 38 Ti-arene 48 Ii-H 367 Ii + -H20 346 Ii -1 igand 244 Ii-He 367 Ii-O 203 Ti-S 203 U-H 367 U--Me 367 U-X 38, 43 V-arene 21 V--CO 279, 281 V-Cp 21

;-V -H20 346 W-alkane 80-82, 85, 86 W-arene 48 w-co 80, 81, 85, 86, 190, 366 W-H 123, 144 W-ligand 243, 244 W-silane 85, 86 Y-arene 48 Y-C2H4 413-416 Y-Cp 14 Zr-C2H4 413-416 Zr-H 367 Zr-llgand 244 Zr-Me 367 Zr-X 39

Bond enthalpy (see also Bond dissociation enthalpy) bond length 3, 6, 7, 189, 191, 204, 205 bond order 189, 333, 337 bond strength 200 contr-ibution (see Bond dissociation enthalpy) dative bonds 337-339, 341, 342 density functional theory 363-367 intrinsic 134, 282, 299, 329-333, 337, 338 polarizability effect 299, 331, 333, 337, 349. 350 potential energy surface 343, 344 promotion energy 282, 283, 299, 327, 329-333, 335-339, 341, 346,

347, 349

spin states 280, 283, 343-345, 398, 400, 401, 407-409, 414, 416 term 132-134, 152, 154-156, 197, 198, 200-205 transferability 72, 134, 189-195, 203, 204

Bond strength (see Bond dissociation enthalpy and Bond enthalpy) Bondi method 160 Born solvation model 245, 264, 265 Bracketing method 236, 241, 254-258, 260

Cadmium alkyl 2, 12, 206, 207 Carbonyl insertion 73, 366, 379-381 Catalytic cycle 39-42, 45-47, 114-116 Center of mass frame 322 Chromium compounds 5, 22-24, 79-92, 119, 122-125, 140, 190, 193,

200, 207, 234, 240, 243, 246, 270, 276, 277, 279, 281, 283, 294-296, 299, 302, 303, 327-340, 342, 345-347, 366, 368, 374

alkane 79-82, 85, 86, 90, 91 amine 82, 83 arene 24, 85, 89, 91, 193, 200, 243 carbonrl 5, 22, 23, 79-92, 190, 193, 234, 243, 279, 366, 368, 374 Cr(CO)n fragments 342, 345 Cr(CO)~ fragments 270, 276, 277, 279, 281 Cr(H20)~ fragments 346, 347 Crl and Crl+ fragments 294-296, 299, 327-340 cyclopentadienyl 24, 243 silane 84-86, 89

Clausius-Clapeyron equation 139 Cobalt compounds 5, 26, 123, 191, 193, 194, 210-213, 217, 239, 240,

246, 256-263, 265, 278, 279, 281, 283, 292, 294-297, 302, 304, 309-312, 316, 318, 319, 327-341, 346, 347, 349, 350, 367, 377-381

acetylene 193, 194 carbonyl 5, 191, 193 CO(CH4~ fragments 347, 349 Co(COln fragments 278, 279, 281, 283 CO(H20)~ fragments 346, 347 Col and Col+ fragments 294-297, 309-312, 316, 327-341, 349, 350 COl2 fragments 311, 312, 339, 341 cyclopentadienyl 26 methylidyne 193

Collision-induced dissociation 269-277, 280, 284, 291, 323, 325, 342, 343, 346, 349-351

Combustion calorimetry 1,2,9-30,131.134-136,198 Cone angle 210-216 Copper compounds 140-144, 294, 302, 318, 327-340, 346, 347

CU(H20)n fragments 346, 347 Cul and Cul+ fragments 294, 327-340

Correlation (sec also Estimation methods) 3-5, 37-39, 43, 151, 183, 242, 244, 327, 329-333, 335-339. 341

Cross section 273-277, 289, 292-296, 322. 324 Cyclic voltammetry 109-112

435

436

Density functional theory 218, 357-381 bond energies 363-367 conformational analysis 369 description of the method 358-363 electron affinity 373-375 excitation energy 370-372 ionization energy 372-373 molecular force fields 375-377 molecular structures 367-369 potential energy surfaces 369 reaction profiles 377-381

Derivative cyclic voltammetry 109-125 kinetic and mechanistic applications 114-120 method 110-113 thermochemical applications 121-125

Differential scanning calorimetry 134 Dimerization of cation radicals 118-120 Diphosphine radical cations 102 Divalent state stabilisation energy 178, 182-184 Double focusing. mass spectrometer 291, 305, 314, 318 Drago equation 216

Electrocatalysis 114-116 Electrochemistry 95-106, 109-125, 233-250 Electrode potential (see also Redox potential) 109, 121-125, 233,

245-248 Electron affinity 218, 233, 235, 238-241, 244, 246-250, 253-255,

258, 260-262, 265, 266, 270, 280, 281, 370, 373-375 acetylacetonates 239, 240 carbonyls 260-262, 270, 280, 281 entropy 249 hexafluoroacetylacetonates 239, 240 substituent effects 240, 241, 247, 249, 261, 262 trifluorophosphines 262

Electron attachment (see Electron affinity) Electron correlation (see also Density functional theory) 387, 389,

418 Electron transfer equilibrium 235-241, 244-246, 248, 249 Electron transfer kinetics 236, 238, 239, 249 Electronegativity 37, 172, 182, 183, 217-223 Electronic chemical potential 217, 218 Electronic factors (see also Bond dissociation enthalpy) 369 Electronic parameter (xl 210 Enthalpy of fusion 159-161, 166, 167

chiral molecules 161 Enthalpy of sublimation 131, 136-144, 159-161, 167, 168 Enthalpy of vaporization 131, 136, 159, 160, 167, 168 Entropy of fusion 161-166

group contributions 161-166 Entropy of reaction 40, 70-72, 173, 181, 236, 239, 249 Equilibrium method 171, 173, 174 Equilibrium studies in solution 53-63, 69-73

Estimation methods (see also Correlation) 159-168, 197-228 enthalpies of fusion 159-161, 166, 167 enthalpies of sublimation 159-161, 167, 168 enthalpies of formation 220-227 enthalpies of vaporization 159, 160, 167, 168

Excited state chromatography 290 Extended HUckel MO method 200, 201

f-Element compounds 13, 14, 35-49, 224, 226, 227, 302, 367, 381, 409

f-Element-metalloid compounds 42-47 Flowing afterglow 269-271, 289, 290, 292

Gallium compounds IS, 240 Germanium compounds 4, 18, 19, 28, 149-153, ISS, 156, 209, 217 Gold compounds 302 Guided ion beam mass spectrometry 172, 321-351

electronic energy 324 instrumentation 322, 323 method 323-325 vibration energy 325, 346

Hafnium compounds 5, 17, 207, 244, 302, 367 Hammett constants 216 Hardness 217, 218 Heterometallic complexes 191, 194 Historical perspective 1-3 Hydration enthalpy 263, 264 Hydrazine radical cations 102 Hydride transfer 96 Hydrocarbon activation (see also Oxidative addition)

287, 288, 294-305, 309-314, 316-319, 322, 339, 392-412

comparison between C-H and C-C activation 392-394 effect of different metals 395-406 effect of the oxidation state of the metal 401-406 ligand effects 406-409 second row transition metals 395-406 ~-bond metathesis 409-412 thermodynamic and kinetic selectivity 55

Hydroamination 40, 41, 49 Hydroformylation 377, 379 Hydrophosphination 40, 42, 49 Hydrosilylation 45, 46, 49, 84

44, 45, 53-67, 351, 388, 389

Ion beam mass spectrometry (see also Guided ion beam mass spectrometry) 287, 289, 290, 292, 294, 305

Ion cyclotron resonance mass spectrometry (IeR and FIleR) 191, 233-236, 238, 239, 241, 244, 245, 256, 287, 289-292, 296, 298

Ionization energy 218, 233, 235, 237-241, 244, 245, 247, 249, 250, 253, 254, 281, 284, 370, 372-373

metallocenes 237-239, 241, 245, 247

437

438

substituent effects 237, 239-241, 247 Ionization entropy 235, 248, 249 Iridium compounds 5, 257, 259, 265, 302, 303, 329, 367, 381, 391,

395 Iron compounds 5, 26, 77, 111, 112, 122, 123, 144, 190-194, 237-239,

240, 243, 244-249, 256-260, 270, 271, 273-276, 278-280, 282, 283, 294, 295, 299, 302, 311-313, 318, 325-344, 346-351, 368, 369, 374, 391, 395

carbonyl 5, 26, 190, 191, 193, 194, 243, 279, 368, 369, 374 cyclopentadienyl 26, 77, 111, 112, 122, 237-239, 243, 245-249,

368, 369, 374 Fe(CH4l~ fragments 347-349 Fe(COl~ fragments 325, 342-344, 348, 349 Fe(COl~ fragments 270, 271, 273-276, 278-280 Fe(H20l~ fragments 346-349 FeL and FeL+ fragments 294, 295, 299, 311-313, 325-341, 349-351 FeL~ fragments 339, 341, 350 methylidene 193 olefin 192, 193, 283 sulphide 194 thiolato 194

Isoelectronic ML fragments 332 Isovalent ML fragments 332

Kinetic energy release distribution 287, 289, 291, 292, 296, 305-317, 341, 342, 350

Kinetic isomers 59, 60 Kinetic method 171, 173-177

iodination method 174-177 Kinetics in the gas phase 171-184 Knudsen effusion 131, 136-139 Kahn-Sham equation 359

Laidler scheme 20, 202-204 Lanthanide compounds (see [-Element compounds) Laser evaporation and ionization 290, 291 Lead compounds 4, 29 Ligand exchange reaction mechanism 79-82, 86, 91, 92, 114-118 Linear sweep voltammetry 113 Lithium compounds 11

M(CH4ln fragments 347-349 M(COl~ fragments 342-345, 348 M(COl~ fragments 269-284 M(H20l~ fragments 345-348

+ ML2 fragments 311, 312, 339, 341, 350 Manganese compounds 25, 30, 84-86, 89, 114-116, 123, 124, 190-192,

203, 206-208, 237, 240, 243, 246, 255-265, 278, 279, 281, 283, 294, 302, 314-316, 318, 327-340, 342, 345-347, 366-368, 371, 379

alkane 85 allyl 192

carbonyl 30, 84-86, 89, 190-192 cyclop~ntadienyl 25, 84-86, 89, 237, 243 Mn(CO)n fragments 314-316, 342, 345 Mn(CO)~ fragments 278, 279, 281 Mn(H20)~ fragments 346, 347 MnL and MnL+ fragments 294, 327-340 silane 84-86, 89

Mean bond dissociation enthalpy (see Bond dissociation enthalpy) Mercury compounds 12, 13, 134, 145, 146, 206, 207 Metal-alkane u complexes 79-82, 84-86 Metal-silane u complexes 83-86 Microcalorimetry 2 Microscopic reversibility 171 Molybdenum compounds 5, 22-25. 30, 79-82, 85, 89, 123-125, 140, 144,

190, 193, 200-205, 207, 215, 224-226, 243, 270, 294. 302, 303. 366, 395-406, 413-416

alkane 79-82, 85 arene 193 car~onyl 5, 22, 23, 79-82, 85, 89, 190, 193. 243. 366 hydride 24, 25, 144 Mo(CO)~ fragments 270 silane 85, 89 thermal decomposition of Mo carbonyl 190

Multiphoton infrared laser activation 291

Nickel compounds 26, 190, 210, 214, 215, 237, 239-241, 243-247, 270. 279, 281, 283, 292-295, 299, 302-304, 318. 327-342, 345-347, 366, 368, 374, 387, 388, 392-394, 412, 416-418

carbonyl 26, 190. 243, 279, 366, 368, 374, 387, 388. 412, 416-418 cyclopentadienyl 26, 237, 239-241, 243-247 Ni(CO)~ fragments 342, 345 Ni(CO); fragments 270, 279, 281 Ni(H20)~ fragments 346, 347 NiL and NiL+ fragments 292-295, 299, 327-341 NiL~ fragments 339, 341

Niobium compounds 21, 294, 301. 302. 395-406, 413-416

Octopole 322 Olefin coordination (see also Olefin insertion) 412-416 Olefin hydroamination 40, 41 Olefin hydrophosphination 40, 42 Olefin hydrosilylation 45, 46 Olefin insertion 39-42, 44-46. 72. 297, 298. 303. 377-379 Osmium compounds 5, 237, 302, 303, 391, 395 Oxidative addition (see also Hydrocarbon activati0n)

alkane 53-67, 84, 339, 366, 381, 391-409 arcne 53-67 hydrogen 366, 381 silane 84

Palladium compounds 294, 302-304, 318, 392-406, 413-416 Periodic trends in atomic metal reactivity 301-304

439

MO

Phase space theory 307-318 Phosphorus compounds 4, 99, 101 Photoacoustic calorimetry 76-79, 176, 191

deconvolution 79 piezoelectric transducer 76

Photoelectron spectroscopy 191, 235, 238, 241, 244, 247, 255, 266, 357, 372, 416

Photomodulation voltammetry 97-99 pKa 96, 121-125, 210, 212-215, 258, 263 Platinum compounds 215, 227, 228, 302, 303 Polarization effects 247 Polycyclic aromatic coordination 55-63 Polymerization of group 14 hydrides 46, 47 Potential energy surface (see also Density functional theory and Bond

enthalpy) 287, 288, 296, 297, 305-307, 310, 313, 317, 318 388, 390, 393, 395-412

Promotion energy (see also Bond enthalpy) 282, 283, 327, 329-333, 335-339, 341, 346, 347, 349

Proton affinity 245 Protonolysis of lanthanide-carbon bond 39, 40 Pulsed high pressure mass spectrometry 235, 236, 239

QALE method 213-215 Quantum chemical methods 357-381, 387-418 Quantum yield 75, 78, 81, 87-91

CO dissociation 81, 87-91

Reaction-solution calorimetry 2, 11-17, 21, 25, 27, 30, 36, 47, 134, 140, 141, 144, 198, 201

Redox potential (see also Electrode potential) 96, 97, 101, 102, 213, 233, 246

Redox reaction 109-125, 233-250 Redox thermochemistry 95-105, 121-125, 233-250

entropy effects 248, 249 substituent effects 247-249

Relativistic effects 363, 390 Reorganization energy 131, 132, 200-204, 206 Rhenium compounds 25, 26, 118, 119, 123, 191, 206-208, 256-263, 302,

367, 391, 395 Rhodium compounds 5, 53-67, 69-73, 257, 259, 260, 265, 294, 301,

2 302, 304, 314, 318, 367, 381, 391, 395-409, 413-416 ~ -a rene 55-63 carbodiimide 65, 66 carbonyl 5 polycyclic aromatic 55-63 porphyrin 69-73 trispyrazolylborate 64-66

Ring resonance 56-63 HUckel energies 57, 63

Ruthenium compounds 5, 116-118, 120, 123, 125, 227, 228, 237, 239, 240, 245-249, 294, 302, 304, 374, 395-406, 408, 413-416

Scandium compounds 13, 14, 240, 293-296, 302-304, 327-341, 409-412 cyclopentadienyl 13, 14 ScL and ScL+ fragments 293-296, 327-341 SCL2 fragments 339, 341

Selected ion flow tube (see also Flowing afterglow) 256 Silane chemistry 171-184 Silane elimination 86 Silicon compounds 3, 4, 6, 7, 27, 28, 84-86, 99, 171-184, 208, 217,

220-222, 227 dimethylsilylene 181-184 halosilylenes 182, 183 silylene 171, 174, 178-184

Silver compounds 294, 302 Solvation 69, 79-92, 100-102, 200, 233, 245-247, 250, 258, 263-266 Solvent cage 88, 89 Spin forbidden process (see also Bond Enthalpy and Spin states)

343-345 Spin saturation transfer 55 Spin states 343-345, 398, 400, 401, 407-409, 414, 416 Steric factors (see also Bond dissociation enthalpy) 132, 134,

154-156, 369 Strain energy (see Steric factors and Bond dissociation enthalpy) Stretching frequency 206-209 Surface ionization 290

21, 302, 303 Tantalum compounds Technetium compounds Thermochemical cycles

302, 367, 395-406, 413-416 95-97, 121-125, 201, 202, 224, 241, 242, 253,

263 Third law method 173, 179, 181 Three electron bond 100, 102 Threshold collisinal activation 350, 351 Tin centered radicals 103-106

electrochemistry 104 homogeneous electron transfer kinetics 104, 105 reaction with nitroalkanes 103, 105, 106

Tin compounds (see also Tin centered radicals) 4, 19, 20, 101, 103-106, 134, 146-148, 151, 152, 154-156

Titanium compounds 5, 15-17, 30, 200-204, 207, 215, 240, 244, 294, 295, 302, 304, 327-341, 346, 347, 367, 410-412

alkyl 5, 16, 244 phenyl 16 Ti(H20)~ fragments 346, 347 TiL and TiL+ fragments 294, 295, 327-341 TiL2 fragments 339, 341

Total phase change enthalpy 166, 167 Total phase change entropy 161-166 Trouton's rule 159, 160 Tungsten compounds 5, 22-25, 30, 79-82, 85, 89, 123-125, 144, 190,

193, 200-204, 207, 243, 244, 270, 296, 298, 302, 303, 366 alkane 80-82, 85 arene 193

MI

442

carbonyl 5, 23, 79-82, 85, 89, 190, 193, 243, 244, 366 hydride 24, 25, 144 silane 85, 89 W(C01~ fragments 270

Unshielded core potential 182, 183, 220

Valence state (see also Promotion energy) 3, 6 Vanadium compounds 21, 237, 238, 240, 246, 278, 279, 281, 283, 294,

295, 302, 304, 327-341, 346, 347, 371 V(C01~ fragments 278, 279, 281 V(H201~ fragments 346, 347 VL and VL+ fragments 294, 295, 327-341 vd fragments 339, 341

Vapour pressure (see Knudsen effusion and Enthalpy of sublimation)

Walden's rule 159, 160, 166

X method 358, 361. 362, 364, 372 0:

yttrium compounds 13, 14, 294, 302, 395-406, 409-416 cyclopentadienyl 13, 14 YL+ fragments 294

Zinc compounds 11, 12, 206, 207, 294, 332 alkyl 11, 12, 206, 207 ZnL and ZnL+ fragments 294, 332

Zirconium compounds 5, 17, 207, 224-227. 244, 294, 302, 367, 395-406, 409-416

ZrL+ fragments 294