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View Considers the IR Spectra of Such Complexes Was Done to Examine the Structure of These Complexes in 1982.31 for Example, It Was Observed That The

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View Considers the IR Spectra of Such Complexes Was Done to Examine the Structure of These Complexes in 1982.31 for Example, It Was Observed That The © 2011 JOANNA M. BERES ALL RIGHTS RESERVED REACTIONS OF SILANES AND CHLOROPHOSPHAZENES WITH HMPA A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Joanna M. Beres August, 2011 REACTIONS OF SILANES AND CHLOROPHOSPHAZENES WITH HMPA Joanna M. Beres Dissertation Approved: Accepted: ______________________________ ______________________________ Advisor Department Chair Dr. Claire A. Tessier Dr. Kim C. Calvo ______________________________ ______________________________ Committee Member Dean of the College Dr. Wiley J. Youngs Dr. Chand Midha ______________________________ ______________________________ Committee Member Dean of the Graduate School Dr. Matthew P. Espe Dr. George R. Newkome ______________________________ ______________________________ Committee Member Date Dr. Peter L. Rinaldi ______________________________ Committee Member Dr. Li Jia ii ABSTRACT The reaction of Si(IV) or P(V) fragments with HMPA will be shown to produce cationic species. Nonmetallic, cationic elements at higher valency are known as onium ions. These onium ions are often highly reactive intermediates. Therefore, we studied them to better understand the synthetic routes in which they are suspected to play a role in. The use of a metal-assisted route will be explored for the formation of siliconium and phosphonium species. The reaction of M(CO)5HMPA with SiR3H in benzene produces a cationic species stabilized by a weakly coordination anion in a liquid clathrate matrix when M is a group six transition metal. The reaction utilizes a one-pot synthesis. The hydrido silanes have been used in this reaction to form stable siliconium + + cations [SiR3(HMPA) ] or [SiR3(HMPA)2 ] that have been proposed intermediates in several organic syntheses. This general synthesis produces a liquid clathrate - through the presence of the weakly coordination anion [(CO)5MHM(CO)5 ]. This anion’s specific geometry seems to be crucial to the formation of the liquid clathrate and therefore the stabilization of the cations. In order to obtain X-ray crystallographic data of the cation an ion exchange reaction was conducted iii + - + - between [SiEt3(HMPA) ][H(W(CO)5)2 ] and K [B(C6F5)4) ]. X-ray crystallographic + + data was obtained for the [SiEt3(HMPA) ][B(C6F5)4 ] complex. Mass + spectrometry was showed the ions [SiEt3(HMPA) ] - + - an [HW2(CO)8 ] for [SiEt3(HMPA) ][H(W(CO)5)2 ]. However, mass spectrometric + - characterization of [SiH2Ph(HMPA)2 ][H(W(CO)5)2 ] showed presence of the [SiPhH(HMPA)Na+] cation due to the sensitivity of the compound. The + decreased stability of the [SiH2Ph(HMPA)2 ] cation is due to the high reactivity of the silicon-hydrogen bond as well as the tendency for five-coordinate silicon compounds to be highly reactive. The generality of this synthesis was investigated and the products were characterized by multi nuclear NMR, ESI-MS and X-ray crystallography. This same metal assisted route was unsuccessful in producing the desired + phosphonium cation [P3N3Cl5(HMPA) ] from [PCl2N]3. This cation is similar to a proposed intermediate in the ring-opening polymerization of [PCl2N]3. However, the reaction of HMPA with a variety of different cyclic chlorophosphazenes was + found to form a different phosphonium cation, [P(NMe2)3Cl ]. A general oxygen/chlorine transfer reaction was observed between the chlorophosphazenes and HMPA resulting in oxygen containing anions. A reaction with minimal byproducts was established for [PCl2N]3 and [PCl2N]4 with + - HMPA resulting in the cationic species [P(NMe2)3Cl ][P3N3Cl5O ] and + - [P(NMe2)3Cl ][P4N4Cl7O ] respectively. The generality of the reaction of iv chlorophosphazenes with HMPA was investigated. The products were characterized by multinuclear NMR, ESI-MS and X-ray crystallography. v ACKNOWLEDGEMENTS First and foremost I must thank my research advisor, Dr. Claire Tessier, for her amazing guidance throughout these past five years. Her general thirst for knowledge is contagious and her intelligence is inspiring. The many late nights that she spent working with me are the only reason that I have made it where I am today. Above all she is a kind, understanding woman whose friendship I will always cherish. Thank you to my committee members: Dr. Youngs, Dr. Espe, Dr. Rinaldi and Dr. Jia for their guidance in this work. Thank you to Dr. Christopher Allen for the donation of [PCl2N]4 to the Tessier laboratory. Thank you to Boulder Scientific for the donation of K[B(C6F5)4]. I would also like to thank my friends. Zin-Min, Dave and Nick have made seemingly dull times in the lab a joy. I will miss all of our conversations over science as well as our laughs over everything else. Anna, I am so thankful that life has brought us back together again. It has been such a comfort having her by my side through this whole experience. I am truly lucky to call her my friend. Thank you also to those teachers who have led me to this point in my life. First, thank you to my parents for being the first teachers of my life. They have vi taught me to value education, to value relationships and to always have faith. Their love and support has meant more to me than they will ever know. Thank you to Mrs. Budd for introducing me to science and giving me the confidence to pursue it. Thank you to Mr. Brovarone for seeing my aptitude for chemistry and challenging me to think beyond the classroom. Thank you to Dr. Walsh and Dr. Freeland for introducing the possibility of graduate school into my future; without their confidence I would not have thought it was possible. Last, but in no way the least, thank you to my husband. Nate has been my rock throughout these past years. I would have never been able to finish this work if it was not for his love and support. He will never know how much I depend on his guidance and companionship. vii DEDICATION to my parents for giving me the tools to complete this degree to my husband for keeping me sane in the process viii TABLE OF CONTENTS Page LIST OF TABLES ................................................................................................... x LIST OF FIGURES ................................................................................................. xi CHAPTER I. INTRODUCTION ................................................................................................. 1 II. SILICONIUM CATIONS IN A LIQUID CLATHRATE MEDIA .............................. 3 2.1 Introduction ............................................................................................ 3 2.2 Experimental .......................................................................................... 28 2.3 Results and Discussion .......................................................................... 35 III. REACTIONS OF CHLOROPHOSPHAZENES WITH HMPA ............................. 55 3.1 Introduction ............................................................................................ 55 3.2 Experimental .......................................................................................... 74 3.3 Results and Discussion .......................................................................... 81 IV. CONCLUSION .................................................................................................. 103 REFERENCES ....................................................................................................... 105 APPENDIX ............................................................................................................. 114 ix LIST OF TABLES Table Page 2.1 X-ray crystal data of [SiEt3HMPA][B(C6F5)4] and W(CO)4(HMPA)2 .............. 33 - 2.2 IR values for [(M(CO)5)2X , BLC = benzene liquid clathrate ......................... 42 o 2.3 Selected bond distances (Å) and angles ( ) of W(CO)4(HMPA)2 ................. 49 + - 3.1 X-ray crystal structure data of [P(NMe2)3Cl ][P3N3Cl5O ], + - + - + - [P(NMe2)3Cl ][P4N4Cl7O ]. [P(NMe2)3Cl ][B(C6F5)4 ] and [P(NMe2)3Cl ]Cl ... 79 3.3 Selection of bond lengths (Å) and bond angles (o) for + - [P(NMe2)3Cl ][P3N3Cl5O ] ............................................................................. 98 + 3.4 Selected bond lengths (Å) for [P(NMe2)3Cl ] ............................................... 101 x LIST OF FIGURES Figure Page 1.1 Examples of siliconium and phosphonium cations ...................................... 2 2.1 The changing geometry and hybridization of silicon as the coordination number increases ........................................................................................ 8 2.2 Depiction of the combination of three sp2 orbitals and a p orbital for five- coordinate SiR4L .......................................................................................... 11 2.3 Simple MO diagram for trigonal bypyramidal molecules such as PF5. Adapted from ref. 13 .................................................................................... 12 2.4 Examples of chiral base promoters synthesizes by Denmark ...................... 15 2.5 Suspected six-membered ring transition state ............................................. 16 2.6 Possible siliconium or neutral intermediates for Equation 2.2 adapted from ref 21............................................................................................................ 18 . 2.7 Ball and stick plot of trans SiCl4 2HMPA from ref. 22 ...................................... 19 . + - 2.8 Ball and stick model of [SiCl3 3HMPA ] HCl2 from ref. 22............................ 20 - 2.9 Examples
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