Fundamental Studies of Early Transition Metal-Ligand Multiple Bonds: Structure, Electronics, and Catalysis Thesis by Ian Albert Tonks In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2012 Defended December 6th 2011 ii 2012 Ian A Tonks All Rights Reserved iii ACKNOWLEDGEMENTS I am extremely fortunate to have been surrounded by enthusiastic, dedicated, and caring mentors, colleagues, and friends throughout my academic career. A Ph.D. thesis is by no means a singular achievement; I wish to extend my wholehearted thanks to everyone who has made this journey possible. First and foremost, I must thank my Ph.D. advisor, Prof. John Bercaw. I think more so than anything else, I respect John for his character, sense of fairness, and integrity. I also benefitted greatly from John’s laissez-faire approach to guiding our research group; I’ve always learned best when left alone to screw things up, although John also has an uncanny ability for sensing when I need direction or for something to work properly on the high-vac line. John also introduced me to hiking and climbing in the Eastern Sierras and Owens Valley, which remain amongst my favorite places on Earth. Thanks for always being willing to go to the Pizza Factory in Lone Pine before and after all the group hikes! While I never worked on any of the BP projects that were spearheaded by our co-PI Dr. Jay Labinger, I must also thank Jay for coming to all of my group meetings, teaching me an incredible amount while I was TAing Ch154, and for always being willing to talk chemistry and answer tough questions. Much thanks also go to my committee: my chairman, Prof. Harry Gray, who played a large part in the intellectual development of the 2nd half of this thesis and treated me as one of his own group; Prof. Bob Grubbs, who is a major reason why I ended up at Caltech and who never fails to embarrass me in front of new people by recounting how Katie tricked me at a bar in Hawaii when we first met; and Prof. Brian Stoltz, who threw me into iv the flames my first term at Caltech in Ch 242, and made me enjoy many aspects of organic chemistry a lot more than I thought I would. In the lab, I’ve had the pleasure of working with over 30 wonderful colleagues and friends. The office dynamic has greatly changed over the years, but one truth remains constant: the Bercaw lab is a strange but wonderful group of people, and I wouldn’t have it any other way. We’ve all gone on adventures in the wilderness on the group hike, spend countless hours in meetings and lab together, travelled the country for conferences, and eaten countless meals together. Everyone in the group has my sincerest gratitude, and since there is no page limit for my thesis I would like to acknowledge everyone individually. First, I would like to thank Prof. Nilay Hazari and Dr. Aaron “ARod” Wilson. When I was on the fence about joining the group, they took me out to Barn Burner, bought me some Shiner, and made me feel incredibly welcome in the group. Throughout my first two years in the group, Nilay served as a mentor for me: he helped me start up the hydrazide project, showed me where the stockrooms were, helped me get my DFT learner’s permit, and was always available for some blunt and realistic advice. Nilay was also the brave soul who shared a tent with Jay on the group hike to the Grand Canyon. ARod was, and still is, one of the nicest, most down to earth people I’ve met in our field. ARod was always down for an adventure—whether it was doing some crazy off-piste skiing or rock climbing, ARod was always willing and able. Prof. Jeff Byers was one of the people that initially—much to his shock, I think— convinced me to join the group. Jeff is an incredibly thoughtful and talented chemist, and I appreciate the time that he took to teach me how to vac transfer and save a box (and v swivel frit, boy) while he was writing his thesis. I’m happy that our friendship has grown since he left the group. Prof. Theo Agapie initiated the non-metallocene project within our group, so I have much to thank him for on the research front. We’ve been extremely fortunate to have such a vibrant and creative young professor join the department as the Bercaw group winds down. Dr. Paul Elowe was my first baymate in 213 North, and I appreciate all the help he gave me as I started to work with the high vac line. Paul was also an excellent teammate on the soccer pitch; our team was never the same once he left for Dow. Also part of the 2006/2007 edition of 213 was Prof. Travis “T-Rav” Williams. Travis was our talented organic postdoc—an endless font of synthetic knowledge and progenitor of the ever-useful “Travis Williams Theory that All Organic Compounds are Colorless.” Travis was a constant source of wry humor, and his group meeting “Travisties” remain legendary. Prof. Dave Weinberg remains a sideburn inspiration to me. Not much else needs to be said about Dave—dude’s just a great guy. The other half of Dave’s “Shaq and Kobe” duo was Dr. George Chen. George always manages to put a positive spin on chemistry when your research is going down the tubes, and was always happy to talk chemistry and Star Wars. Dr. Bolin Lin was a wonderful TA for organometallics, and also full of surprises—after one vacation, he came back married! Dr. Suzanne “Bulldog” Golisz was always a social hub of the group; thanks for being such a gracious host and inviting us all to football parties, Halloween parties, and the like. Good luck up at Brookhaven! Dr. Valerie Scott always had one of the best attitudes in the group, and you can always count on Val for a good laugh or a great story (or bizarre pictures of cartoon bunnies!). Luckily, we still get Val dropping by every now and then from her postdoc at JPL. vi An extra special thanks goes to Dr. Sze-Man Yu for a special delivery of the 10 g of HgMe2 and 10 g CdMe2 that we recently received. Dr. Melanie Zimmerman, a visiting scholar in the group, was a great source of knowledge for all things Group 3, and helped me get involved in a few scandium and yttrium projects. Prof. Ned West, Prof. Alex Miller, and Dr. Steve Baldwin could always be counted on to get a soda sometime between 2:00-3:00 every day. On top of being great break folks, these three all contributed greatly to my scientific and personal growth. Alex was my office neighbor for 4 years and was great to bat ideas around with; Steve was an early transition metal co-conspirator and late night lab partner, and Ned was a wonderful labmate in 213 North who seemed to pretty well tolerate my messes and the general “lameness” of the lab. Thanks guys. During my stay we’ve had 6 solid undergraduates working in the lab. Koyel Bhattacharyya, who worked with Bolin, was a ball of energy in the lab, and continues to work hard up at Stanford in grad school. Daniel Tofan, who started the NNN project, is currently working with Kit Cummins at MIT; thanks for giving us a great start on that project! “Little” Alex Velian, who worked with Big Alex and Theo, is one of the happiest undergrads I’ve ever met from Caltech, and is also now part of the Caltech-MIT undergrad-grad exchange. She is also deathly afraid of snakes. Yuxiao Sun worked with Matt Winston, and will be starting grad school now-ish. Good luck! I had the great fortune of having 2 wonderful young scientists as my mentees. First, Josef Meier, from TU-Munich, worked with me on the ONO hydroamination project. On top of being an enthusiastic (and successful!) chemist, Josef was a great friend to the whole group. His love of a good burger drove us to some excellent restaurants. Tonia vii Ahmed from WVU worked with me on the indene C-H activation project, and was likewise extremely excited about doing research and getting into the Caltech life. Working with these students has been extremely rewarding, and I hope they learned half as much as I did working with them. Good luck to you both going forward. My two classmates, Dr. Paul Oblad and Dr. Ted Weintrob, were with me all the way. We were lucky to get the both of you from Jonas’ group before he left! Paul is a certified scout, and was super clutch to have along on all the group hikes. He also has some absolutely crazy stories about blowing up 3 liter bottles filled with chemicals in the middle of lakes! Ted and I started undergrad at Columbia together, worked for Ged Parkin together, and then came to Caltech together and (circuitously) ended up in the Bercaw group together. Ted was my go-to guy early on for all the stupid questions that I was too afraid to ask anyone else, a constant night-shift lab presence, and an all around good guy. I’m happy to count him amongst my friends. We’ve learned together, struggled together, played sports together, and now it’s time to strike out on our own.