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Bell & Howell Information and Learning 300 Nom Zeeb Road, Ann Arbor, MI 48106-1346 USA Intramolecular Proton-Hydride Interactions in Iridium Complexes - a New Type of Hydrogen Bond Sung Han Park A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy in the Graduate Department of Chemistry University of Toronto O Copyright by Sung Han Park 1998 National Library Bibliotheque nationale 191 of Canada du Canada Acquisitions and Acquisitions et Bibliographic Services services bibliographiques 395 Wellington Street 395, rue Wellington Ottawa ON K1A ON4 Ottawa ON K1A ON4 Canada Canada The author has granted a non- L'auteur a accorde une licence non exclusive licence allowing the exclusive pennettant a la National Library of Canada to Bibliotheque nationale du Canada de reproduce, loan, distribute or sell reproduire, preter, distribuer ou copies of thls thesis in microfom, vendre des copies de cette these sous paper or electronic formats. la forme de microfiche/film, de reproduction sur papier ou sur format electronique . The author retains ownership of the L'auteur conserve la propriete du copyright in thls thesis. Neither the droit d'auteur qui protege cette these. thesis nor substantial extracts ~ornit Ni la these ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent &treimprimes reproduced without the author's ou autrement reproduits sans son permission. autorisation. Abstract Seven cationic hydrido pyridinethione (SpyH) complexes containing either PCy3 or PPh3 co-donor ligands have been prepared from iridium polyhydride complexes. These include three PCy3 complexes [IrHi(q -SP~H)~(PC~~)~1 ( BFj) I. [IrH(q - SpyH)4(PCy3)1(BF4)24, [IrH(q i-SpyH)2(q2-Spy)(PCy3)l(BF4)5 and four PPh3 complexes [IrH(q l-~py~)(q~-spy)(~~h~)~](~~~)9. [IrHz(q l-spy~)(~~h~)~](BFj) 10. [IrHr(q 1-SpyH)2(PPh3)2](BF4)11 and [IrH(CO)(ql-S~yH)~(P~h3)21(BF?)2 12. All contain NH--HIr proton-hydride bonding units in the solid state {d(HH): 1.8 to 2.1 A. X- ray analysis}. The proton-hydride bonds in these complexes are maintained in CH2Clz. Stronger proton-hydride bonds are formed in complexes with PCy, co-donor ligands vs complexes with PPh3 co-donor ligands. The strength of proton-hydride bonds is decreased in complexes containing more PPh3 or CO ligands. The strength of the proton-hydride bonds in solution is probed for 1.1 and 5 by introducing a conventional H-bond acceptor (THF-dxor OPPh3). The H-H interactions in 1 are disrupted but remain intact in 4 and 5. Four chloro SpyH complexes cis-IrH2Cl(q l-~pyH)(~Cy~)~13. IrI-ICI?(q - SpyH)(PCy3)2 14a. IrClz(ql-SpyH)(q2-Spy)(pCy3)IS and [IrCl(qI-~py~)~(q2-~py) (PCy3)](BF4)16 have been prepared from iridium polyhydride complexes. 13 and 14a contain NH--CIIr hydrogen bonds over NH- .HIr bonds d(H-421): 2.15(7) A. 15 ). 16 possesses an N-H-Cl(1r)---H-N hydrogen bonded network {d(N.-CI): 3.137, 3.045 A}. Ligmds other than HSpy used in the reaction with IrH5(PCy3):! include pyrazole. acetaldoxime and dirnethylglyoxime. The products of these reactions are iridium(l1I) dihydrides containing conventional Y-H-X hydrogen bonding units, Y. X = N. 0. An 18 electron Ir(II1) complex containing IrS.*FBF3and agostic Ir-H-C bonds is formed in the reaction of IrH5(PCy3)2 with HBF4 in benzene {d(Ir--HI: 2.04(5) A and d(Ir---F):2.172(3) A } . Mom and Dad, how wonde~$ulit is to be your son. Your never-ending love has made it all possible. For Hee Ymng & Swzg Ji Harmah Acknowledgments The very first and foremost person I would like to express my sincere thanks to is my supervisor Robert H. Morris for his never-ending guidance and patience during the past years. He and his wife Colleen have always been there to encourage us whenever we encountered a light or heavy storm ! I thank Dr. Ravindranath Ramac handran for his initial introduction to the proton- hydride bonding complexes. Much of his effort was devoted to the very first paper on this topic we published in the Journal of the American Chemical Society. I am grateful to Drs. Wei Xu and Dmitri Goussev for their valuable thoughts and discussion regarding the proton- hydride bond and Marcel Schlaf and Cameron Forde for their advice and comments on dihydrogen chemistry. The former and present group members who have contributed in various ways include Dr. Kamaluddin Abdur-Rashid. Erin Baker. Tina Fong, Shaun Landau, Adrian Lee. Sandra Trentowsky, Tanya Bartucz, Edward Lueng. Bernhard Otto. Thomas Schleis and Patrick Amhein. I am indebted to Kamaluddin Abdur-Rashid, Erin Baker. Shaun Landau. Sandra Trentowsky and Avinash N. Thadani for their proofreading. I thank Nick Plavac for his valuable NMR experiments and Dr. Timothy S. Burrow for his diligent and cheerful assistance with the NMR spectrometers. Alan Lough's outstanding skill in X-ray spectrometry made it possible to understand many of proton- hydride bonding species. Other chemistry department colleagues Alex Young (FAB-MS studies). Ron Legge (Glass blowing) and Dan Mathers (instruments) are also thanked for their helpful assistance. Finally. I would like to thank my loving family. Hee Young Nah and Sung Ji Hannah Park for their love and patience until we are here. List of Abbreviations acdxd ace taldoxime bqH 7,8-benzoquinoline CP cyclophentadieny 1 dppe 1.2-bis(diphenylphosphino)ethane dppm bis(dipheny1phosphino)methane en e thy lenediamine ether diethyl ether glxmH2 dimethylglyoxime fCy3 tricyclohexylphosphine PPh3 triphenylphosphine PYOH 2-hydroxypyridine P~H pyrazole QAMD quinolineacetamide SALEN N. N'-ethylenebis(sa1idene iminato) SPYH Zpyridinethione or 2-mercaptopyridine SPY Zpyridinethiolate THF te trahydro furan CSD Cambridge Structural Data COSY Correlation Spectroscopy FAB MS fast atom bombardment mass spectrometry IR Infrared NMR Nuclear Magnetic Resonance NOE NucIear Overhauser Effect RT room temperature TI spin-lattice relaxation time Vr variable temperature Compound numbering Scheme Table of Contents Abstract ......................................................................................il ... Dedication ............................................................................. 111 Acknowledgments .......................................................................... v List of Abbreviations .......................................................................vi Compound numbering Scheme ........................................................... vii Table of Contents ........................................................................... vii List of Figures .............................................................................. xi 1 List of Schemes ............................................................................ xviii List of Tables ............................................................................... xix Chapter 1 . The hydrogen bond in transition metal complexes ......................... 1.1. Conventional or classical hydrogen bond ......................................... 1.1.1. History and definition ............................................................. 1 .l.2. Geometry of conventional hydrogen bonds .................................... 1.1.3. Classification of secondary bonds involving hydrogen in transition metal compounds .................................................................................. 1.2. Non-classical MH-MY hydrogen bond: the proton-hydride bond ............. 1.2.1. Speculation about M-Hm'.H-Ybonding before its discovery .................. 1.2.2. The discovery of short proton-hydride bonds .................................. 1.2.3. Bonding ................................................ , ......................... 1.3. Preparation of species containing a proton-hydride bond ....................... 1.3.1. Oxidative addition .................................................................. 1.3.2. Substitution reaction ............................................................... 1.3.3. Ring-opening reaction ............................................................. 1.3.4. Substitution of polyhydride complexes ......................................... 1 .4. Characterization of proton-hydride bonding ...................................... 16 1.4.1. Infrared spectroscopy ............................................................