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Mechanistic Insights Into Alkane C-H Activation and Functionalization by Metal Oxide Surfaces and Organometallic Complexes

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Mechanistic Insights Into Alkane C-H Activation and Functionalization by Metal Oxide Surfaces and Organometallic Complexes Mechanistic Insights into Alkane C-H Activation and Functionalization by Metal Oxide Surfaces and Organometallic Complexes Thesis by Mu-Jeng Cheng In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2012 (Defended May 18, 2012) ii 2012 Mu-Jeng Cheng All Rights Reserved iii To my family and my wife iv ACKNOWLEDGEMENTS My Ph.D. journey is enriched and completed by the presence of several important individuals who help me either in my research or in my daily life, and accompany me through happiness and sadness of my days at Caltech. It is my great pleasure to acknowledge their support. First, I would like to thank Prof. William A. Goddard III. I am extremely grateful to have Bill as my research advisor. During my entire Ph.D., Bill has always been very supportive and patient in guiding me and training me to become a better scientist. I have learned a great deal of knowledge from him in terms of how to choose a good research topic and how to execute and complete a project. I could not have accomplished what I have without him. I would like to thank my thesis committee members: Prof. Harry Gray, Prof. Robert Grubbs, Prof. James Heath, and Prof. Aron Kuppermann. My committee is immensely supportive and helpful in giving me both excellent suggestions and encouragement. Especially, I would like to thank Prof. Aron Kuppermann for helping me and my family to go through the saddest days of our life. I am very indebted to the current and former members in the Goddard group. I would like to thank Robert Nielsen (Smith) for being a good mentor, collaborator, and friend. I will forever remember the enormous time he spent to teach me scientific writing, computational chemistry, and organometallics. I would like to thank Jonathan Mueller and Hyungjun Kim for being my good friends, classmates, and colleagues. I would like to v thank Julius Su, Tod Pascal, Jonas Oxgaard, Kimberly Chenoweth, Adri van Duin, and Andres Jaramillo-Botero for their help in my research. I also would like to thank Patrick Theofanis, Qi An, Hai Xiao, Vaclav Cvicek, Wei-Guang Liu, Fan Liu, Himanshu Mishra, and Ross Fu. Their participation enriched my days in the Goddard group. I would like to thank my collaborators, Prof. John Groves, Wei Liu, Prof. Periana, and Steven Bischof. I have learned a great deal of knowledge about alkane functionalization chemistry (radical or nonradical approach) from them. I would like to acknowledge Chevron-Texaco Energy Research and Technology Company and the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center, for supporting me financially. I would like to thank my friends in the Taiwanese student community at Caltech: I-Ren Lee, Hsuan-Tien Lin, Bor-Ching Su, Chia-Chieh Chu, Chun-Yang Chen, Chi-Hao Liu, Jen-Kan Yu, and Tsui-Fen Chou. The time we shared brought a lot of fun to my Ph.D. journey. I will always remember the day that I-Ren Lee and Hsuan-Tien Lin picked me up from LAX and helped me to setup when I arrived in LA at June 30th 2005. I would like to thank my parents and my parents-in-law for their support and encouragement. I would like to thank my brother and sister for taking care of my father. Finally and most importantly, I would like to thank my wife Kuang-Jung Chang for accompanying me and making my Ph.D. a wonderful voyage. vi ABSTRACT Alkanes are the major components of natural gas and petroleum; however, there are only few practical processes that can functionalize them into more valuable products such as alkene or alcohols. The reason for this difficulty is because alkanes possess strong and inert C-H bonds. The development of such a process that can convert alkanes to other more valuable functionalized hydrocarbons in a catalytic fashion would produce enormous economic benefits. The key to achieve this goal is to develop a proper catalyst. The catalysts can be organometallic complexes or metal oxide surfaces that catalyze alkane C-H activation and functionalization in homogeneous or heterogeneous conditions. In this thesis, we apply quantum mechanics to study the known alkane functionalization reactions to provide more insight into those catalytic processes, and we further utilize our computational results to design new reaction pathways for alkane functionalization. Each chapter presented herein constitutes an independent publication focusing on different aspects of the problem. Chapter 1: Single-Site Vanadyl Activation, Functionalization, and Reoxidation Reaction Mechanism for Propane Oxidative Dehydrogenation on the Cubic V4O10 Cluster: Vanadium oxide is a powerful heterogeneous catalyst that can convert oxidative dehydrogenation vii (ODH) of propane. Despite numerous studies, either computational or experimental, on this topic, no complete catalytic cycle is provided. In this paper, we examined the detailed mechanism for propane reacting with a V4O10 cluster to model the catalytic oxidative dehydrogenation (ODH) of propane on the V2O5(001) surface. We reported the mechanism of the complete catalytic cycle, including the regeneration of the reduced catalyst using gaseous O2, in which only a single vanadyl site is involved. This mechanism is applicable to propane ODH on the supported vanadium oxide catalysts where only monovanadate (O=V-(O)4-) species is present. Chapter 2: The Magnetic and Electronic Structure of Vanadyl Pyrophosphate from Density Functional Theory: We have studied the magnetic structure of the high-symmetry vanadyl pyrophosphate, focusing on the spin exchange couplings, applying density functional theory with exact exchange and the full three-dimensional periodicity to this system for the first time. Based on the local density of states and the response of spin couplings to varying the cell parameter a, we found that two major types of spin exchange couplings originate from different mechanisms: one from a super-exchange interaction and the other from a direct exchange interaction. Based on the variations in V–O bond length as a function of strain along a, we found that the V–O bonds of V–(OPO)2–V are covalent and rigid, whereas the bonds of V– (O)2–V are fragile and dative. Chapter 3: The Para-Substituent Effect and pH-Dependence of the Organometallic Baeyer-Villiger Oxidation of Rhenium-Carbon Bonds: viii Organometallic Baeyer-Villiger represents another means of oxidizing M-R to M-OR. In this work, we conducted a series of calculations with the goal of providing more insights into the reaction. We find that during this organometallic BV oxidation, the migrating phenyl plays the role of a nucleophile and the leaving group OH is nucleophile. Moreover, we also find that for R = Ph the reaction rate is much faster than that for R = Me, which is later confirmed by experiments. Chapter 4: Carbon-Oxygen Bond-Forming Mechanisms in Rhenium Oxo-Alkyl Complexes: Intramolecular 1,2-migration of hydrocarbyl across metal-oxo bonds is one of the few means of oxy-functionalizing M-R to M- OR bonds. This strategy works for R = Ph, but fails for R = Me and Et. In this work, we study these systems with the goal of understanding the reason. We find that when R = Me and Et the -hydrogen is very acidic and easy to abstract even with weak base, such as the counter ion of the complex, leading to unwanted by-products. We find that these side reactions can be avoided by two means: (1) use counter ions with weaker basicity to increase proton abstraction barriers, and (2) use R = iPr, which has a higher migratory aptitude, to accelerate the 1,2-migration rate. Chapter 5: A Homolytic Oxy-Functionalization Mechanism: Intermolecular Hydrocarbyl Migration from M-R to Vanadyl Oxo: Oxy- functionalization M+-R- to M-OR bonds is one of the key challenges in the development of hydrocarbon hydroxylation catalysts. This can be achieved by ix limited means: (1) organometallic Baeyer-Villiger oxidation, and (2) intramolecular 1,2-migration of hydrocarbyl across metal-oxo bonds. In this work, we have examined C-O bond formation in the reaction of OVCl3 with Ph2Hg to generate phenol using quantum mechanics. Surprisingly, we find this reaction is through an unprecedented bimolecular, one-electron oxidation of the V-Ph bond by a second V=O moiety, not through the experimentally proposed intramolecular phenyl 1,2-migration across V=O bonds. Our calculations on the oxidation of Rh-CH3 and Ir-CH3 complexes by OVCl3 further suggest that the possibility of integrating this new oxidation mechanism into alkane oxidation catalytic cycles. We also give guidelines to choose the systems in which this oxidation mechanism may play an important role. x TABLE OF CONTENTS Acknowledgements ............................................................................................ iv Abstract ............................................................................................................... vi Table of Contents ................................................................................................. x List of Tables .................................................................................................... xiii List of Figures ................................................................................................... xiv Chapter 1: Single-Site Vanadyl Activation, Functionalization, and Reoxidation Reaction Mechanism for Propane Oxidative Dehydrogenation on the Cubic V4O10 Cluster ................................................ 1 1.1 Introduction ......................................................................................
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