Surface And Interfacial Organometallic Chemistry And Catalysis

by Coperet, Christope; Chaudret, Bruno; Basset, J. M. (CON); Bonino, F. (CON); Bordiga, S. (CON)

• ISBN13: 9783540264965
• ISBN10: 3540264965
• Format: Hardcover
• Copyright: 2005-12-16
• Publisher: Springer Verlag

Summary

Heterogeneous catalysis has been essential to the development of efficient chemical processes for more than a century, and this field has been traditionally part of the solid state chemistry and surface science communities. The design of better catalysts has raised the following questions: "what is the structure of the active sites?" and "how to control their nature?" The necessary need to develop more sustainable chemical processes and the success of homogeneous catalysis relying on molecular organometallic chemistry has led the community of molecular chemists to investigate the preparation of single-site heterogeneous catalysts. The authors discuss the molecular design, the preparation, the characterisation and the catalytic applications of well-defined oxides and metal particles. The readers will acquire a molecular understanding of heterogeneous catalysis, which will help them develop a critical view and which will attract them to study this fascinating field.

Table of Contents

Anatomy of Catalytic Centers in Phillips Ethylene Polymerization Catalyst
A. Zecchina, E. Groppo, A. Damin, C. Prestipino	1	(36)
1 Introduction	2	(2)
2 Spectroscopic Characterization of the Catalyst	4	(15)
2.1 Surface of the Silica Support	4	(3)
2.2 Anchoring Process and Structure of Anchored Cr(VI)	7	(3)
2.3 Reduction Process and Structure of Reduced Chromium	10	(9)
2.3.1 Oxidation State of Reduced Chromium	10	(1)
2.3.2 Structure of Cr(II) Sites	11	(8)
3 Catalytic Activity and Polymerization Mechanism	19	(11)
3.1 Active Sites and Turnover Number	20	(1)
3.2 First Spectroscopic Attempts to Determine the Polymerization Mechanism	21	(2)
3.3 Polymerization Mechanisms Proposed in the Literature	23	(19)
3.3.1 Ethylene Coordination, Initiation and Propagation Steps	23	(2)
3.3.2 Standard Cossee Model for Initiation and Propagation	25	(1)
3.3.3 Carbene Model for Initiation and Propagation	26	(1)
3.3.4 Metallacycles Model for Initiation and Propagation	26	(2)
3.3.5 Conclusions and Future Improvements	28	(2)
4 Open Questions and Perspectives	30	(2)
References	32	(5)
Single Site Catalyst for Partial Oxidation Reaction: TS-1 Case Study
S. Bordiga, A. Damin, F. Bonino, C. Lamberti	37	(32)
1 Introduction	38	(2)
2 Oxidation Reactions Catalyzed by TS-1	40	(2)
3 Investigation of the Bare TS-1: Anhydrous Catalyst	42	(8)
3.1 XRD	43	(1)
3.2 UV-Vis	44	(1)
3.3 XANES	45	(1)
3.4 EXAFS	45	(1)
3.5 IR	45	(1)
3.6 Raman	46	(1)
3.7 Resonant Raman	46	(2)
3.8 The Defective Nature of TS-1 Material: Speculative Model of Framework Sites	48	(2)
4 TS-1 in Interaction with Ligand Molecules	50	(5)
4.1 Interaction with Water and Ammonia	50	(4)
4.1.1 UV-Vis	50	(1)
4.1.2 XANES and EXAFS	51	(1)
4.1.3 IR	52	(1)
4.1.4 Raman and Resonant Raman	52	(2)
4.1.5 Adsorption Microcalorimetry	54	(1)
4.2 Interaction With Other Molecules	54	(1)
5 TS-1 Interaction With H2O/H2O2 Solutions	55	(10)
5.1 General Overview	55	(3)
5.2 New Advances from Resonant Raman Spectroscopy	58	(3)
5.3 Equilibria between Peroxo and Hydroperoxo species in the TS-1/H2O2/H20O System: In Situ UV-Vis DRS and High Resolution XANES Highlights	61	(4)
References	65	(4)
Tailored Oxide Materials via Thermolytic Molecular Precursor (TMP) Methods
K.L. Fujdala, R.L. Brutchey, T.D. Tilley	69	(48)
1 Introduction	70	(3)
1.1 History and Scope of this Review	73	(1)
2 Synthetic Aspects	73	(17)
2.1 Ligand Precursors	74	(1)
2.2 LnM[OxSi(OtBu)y]z Molecular Precursors	75	(9)
2.2.1 Groups 1-2	75	(1)
2.2.2 Group 4	76	(1)
2.2.3 Group 5	77	(2)
2.2.4 Group 6	79	(1)
2.2.5 Group 8	80	(1)
2.2.6 Group 9	81	(1)
2.2.7 Group 10	81	(1)
2.2.8 Group 11	81	(1)
2.2.9 Group 12	82	(1)
2.2.10 Group 13	83	(1)
2.2.11 Groups 14-15	84	(1)
2.3 LnM [O2P(OtBu)2]x Molecular Precursors	84	(3)
2.3.1 Group 4	84	(1)
2.3.2 Group 5	85	(1)
2.3.3 Group 6	85	(1)
2.3.4 Group 12	86	(1)
2.3.5 Group 13	86	(1)
2.4 LnM(OB[OSi(OtBu)3]2}x Molecular Precursors	87	(1)
2.4.1 Group 4	87	(1)
2.4.2 Group 6	88	(1)
2.5 Molecular Precursors Containing Combinations of - OSi(OtBu)3, - O2P(OtBu)2, and - OB[OSi(OtBu)3]2 Ligands	88	(2)
3 Mechanistic Insight into the Decomposition of Oxygen-Rich Molecular Precursors	90	(1)
4 Solid Phase and Solution TMP Methods	91	(11)
4.1.1 Thermolytic Conversion of Group 2 Siloxide Precursors	91	(1)
4.1.2 Thermolytic Conversion of Group 4 Siloxide Precursors	92	(1)
4.1.3 Thermolytic Conversion of Group 5 Siloxide Precursors	93	(2)
4.1.4 Thermolytic Conversion of Group 6 Siloxide Precursors	95	(1)
4.1.5 Thermolytic Conversion of Group 8 Siloxide Precursors	96	(1)
4.1.6 Thermolytic Conversion of Siloxide Precursors of Groups 9-12	97	(1)
4.1.7 Thermolytic Conversion of Group 13 Siloxide Precursors	98	(1)
4.2 Thermolytic Conversion of Di(tert-butyl)phosphates	98	(2)
4.3 Thermolytic Conversion of Ln,M{OB[OSi(OtBu)3]2}x Molecular Precursors	100	(1)
4.4 Thermolytic Conversion of Mixed Ligand Species	101	(1)
5 TMP Routes to Mesoporous, Multicomponent Oxides	102	(1)
6 TMP Routes to Hybrid Inorganic/Organic Materials	103	(2)
7 CVD Applications of Single-Source Molecular Precursors	105	(1)
8 Molecular Precursor Grafting Methods	106	(3)
8.1 Site-Isolated Ti(IV) Centers	107	(1)
8.2 Site-Isolated Fe(III) Centers	108	(1)
8.3 Site-Isolated Cu(I) Centers and Cu Nanoparticles	109	(1)
9 Summary and Future Directions	109	(1)
References	110	(7)
Spectroscopic Characterization of Organometallic Centers on Insulator Single Crystal Surfaces: From Metal Carbonyls to Ziegler-Natta Catalysts
T. Risse, H.-J. Freund	117	(34)
1 Introduction	118	(1)
2 Metal Carbonyls on a Well Defined Alumina Surface	119	(11)
2.1 Small Metal Particles and Single Metal Atoms	120	(7)
2.2 Carbonyl Species on Metal Particles	127	(3)
3 Ziegler-Natta Model Catalyst	130	(15)
3.1 MgCl2 Thin Film as a Model Support	131	(2)
3.2 Adsorption of TiCl4	133	(4)
3.3 Activation of the Catalyst	137	(3)
3.4 Polymerization of Ethylene and Propylene	140	(5)
4 Conclusions	145	(1)
References	145	(6)
Analogy between Surface and Molecular Organometallic Chemistry
J.-P. Candy, C. Copéret, J.-M. Basset	151	(60)
1 Surface Organometallic Chemistry	152	(1)
2 Surface Organometallic Chemistry on Oxide Supports	153	(32)
2.1 Reaction of Organometallic Complexes with Oxide Supports: the Controlled Formation of Surface Organometallic Complexes	153	(16)
2.1.1 Step 1: Characterization of the Support	153	(1)
2.1.2 Step 2: Mass Balance Analysis and Mechanistic Studies on the Grafting Step	154	(7)
2.1.3 Step 3: Characterization of the Grafted Species Through Advanced Spectroscopic Techniques	161	(5)
2.1.4 Step 4: Chemical Reactivity of Surface Complexes	166	(3)
2.1.5 Conclusion	169	(1)
2.2 Catalytic Reactions and Elementary Steps	169	(16)
2.2.1 Oxidation, Transesterification and Related Reactions	169	(1)
2.2.2 Olefin Metathesis	170	(5)
2.2.3 Alkane Hydrogenolysis	175	(4)
2.2.4 Alkane Metathesis	179	(5)
2.2.5 The Cross-Metathesis of Propane and Methane	184	(1)
2.2.6 Conclusion	184	(1)
3 Surface Organometallic Chemistry on Metal Particles	185	(19)
3.1 Reaction of Organometallic Complexes with Particles of Transition Elements: The Stepwise Hydrogenolysis of Metal-Carbon Bonds	185	(10)
3.1.1 Tetraalkyl Compounds of the Group 14 Elements, the Case of SnBu4	187	(4)
3.1.2 Triphenyl Compound of Group 15 Elements, the Case of AsPh3	191	(2)
3.1.3 Diphenyl Compound of a Group 12 Element, the Case of HgPh2	193	(2)
3.1.4 Conclusion	195	(1)
3.2 Catalytic Reactions and Elementary Steps on Metallic Surfaces	195	(18)
3.2.1 Carbon-Carbon Bond Cleavage on Metallic Surfaces	195	(4)
3.2.2 Taming Carbon-Carbon Bond Cleavage on Metallic Surfaces, the "Site Isolation" Effect	199	(2)
3.2.3 Selective Reactions on Modified Metal Surfaces: the Ligand Effect	201	(1)
3.2.4 Selective Reactions on Modified Metal Surfaces: Adatom Effect (Selective Site Poisoning)	202	(1)
3.2.5 Selective Reactions on Modified Metal Surfaces: The Case of Alloys	203	(1)
3.2.6 Conclusion	203	(1)
4 General Conclusion	204	(1)
References	205	(6)
Oxide- and Zeolite-supported "Molecular" Metal Clusters: Synthesis, Structure, Bonding, and Catalytic Properties
B.C. Gates	211	(22)
1 Introduction	211	(2)
2 Chemistry of Supported Metal Clusters	213	(16)
2.1 Monometallic Clusters	213	(22)
2.1.1 Synthesis of Metal Carbonyl Clusters and Decarbonylated Clusters	213	(11)
2.1.2 Bimetallic Clusters	224	(2)
2.1.3 Reactivity and Catalysis	226	(3)
References	229	(4)
Synthesis and Surface Reactivity of Organometallic Nanoparticles
B. Chaudret	233	(28)
1 Introduction	234	(1)
2 Organometallic Synthesis of Metal Nanoparticles	235	(7)
2.1 Surface Characterization	238	(4)
2.1.1 Infrared Spectroscopy	238	(1)
2.1.2 NMR Spectroscopy	239	(2)
2.1.3 Magnetic Measurements	241	(1)
3 Surface Organometallic Chemistry on Nanoparticles	242	(7)
3.1 Active Ligands	243	(1)
3.2 Ancillary Ligands	243	(5)
3.2.1 Alcohols	243	(2)
3.2.2 Amines	245	(1)
3.2.3 Thiols	246	(1)
3.2.4 Phosphines	247	(1)
3.3 Directing Ligands	248	(1)
4 Organization of Nanoparticles	249	(2)
4.1 Hydrogen Bond Network	249	(1)
4.2 Self-organization	250	(1)
4.3 Crystallization	250	(1)
5 Shape Control of Nanoparticles	251	(5)
5.1 Confinement in a Mesoporous Silica	252	(1)
5.2 Use of Long Chain Organic Ligands	252	(4)
6 Conclusion	256	(1)
References	257	(4)
Stabilized Noble Metal Nanoparticles: An Unavoidable Family of Catalysts for Arene Derivative Hydrogenation
A. Roucoux	261	(20)
1 General Aspects	262	(4)
1.1 Arene Hydrogenation	262	(1)
1.2 Nanoparticle Concepts	263	(3)
1.2.1 Electrostatic Stabilization	264	(1)
1.2.2 Steric Stabilization	264	(2)
2 Total Hydrogenation by Protected Nanocatalysts	266	(8)
2.1 PVP Stabilization	266	(1)
2.2 Stabilization in Ionic Liquids	267	(3)
2.3 Stabilization by Polyoxoanion	270	(1)
2.4 Stabilization by Surfactant	271	(3)
3 Partial Hydrogenation by Nanocatalysts	274	(2)
3.1 Polyoxoanion-Stabilized Rh(0) Nanoclusters	275	(1)
3.2 Ionic Liquids-Protected Ru(0) Nanoparticles	276	(1)
4 Conclusion	276	(1)
References	277	(4)
Author Index Volumes 1-16	281	(8)
Subject Index	289