Note to reader:  Much of the information here is contained in my dissertation, copies of which can be found at both the science library as well as polymer science department at U. Akron.

I spent the remainder of my academic career working in the Collins’ lab.*  It was here that I actually learned the majority of my laboratory skills.  Most of these skills were not imparted by the teachings of people in this lab but instead were self-taught by reading texts such as “The Manipulation of Air-Sensitive Compounds” followed with repeated trial and error attempts to replicate what I had read.  Once I entered this research group the first task at hand was to synthesis a compound that was nicknamed “holy grail.”  This material was a perfluoroarylated chelating (i.e. bidentate) borane that has the formula 1,2-C₆F₄[B(C₆F₅)₂]₂ and it proved at that time to be very difficult to make (taking the better portion of one year).  During this period I made some minor improvements to the synthesis of this compound.  Several things stood out in stark contrast to my experience in “Kennedy’s” lab.

1. Collins’ equipment was modern (please see pictures below, which only show a portion of modern pieces of equipment).
2. Scott was well-versed in the types of manipulations that needed to be conducted and was excellent at deciphering NMR spectra.
3. Scott was a stickler for only publishing chemistry that was replicable and I can’t ever imagine him attempting to fabricate anything.
4. Dr. Collins also was a slave driver, and in that regard I learned to develop an even better work-ethic than I had before.

Grubb’s Still for purification of solvents.

IB being collected in a graduated tube on a specialized Schlenk line.

BBr3 being purified.

Next, I began exploration of the polymerization of IB under anhydrous conditions using “holy grail” as many analogous monodentate perfluoroarylated Lewis acids had been previously used in a similar manner.  It was not uncommon for me to spend 10-12 hour days, every day of the week working in an attempt to get my degree.  In addition to the synthesis of “holy grail” and the numerous other compounds had to be made (e.g. initiators, surfactants, etc.) just for polymerization studies, a large amount of time was devoted towards conducting modeling experiments.  During my stint in this lab I collected in excess of 1,000 NMR spectra (see picture below) and many experiments were quite time consuming (ca. 6-8 hours) where manual probe tuning between ¹H and ¹⁹F nuclei had to be conducted (in addition to manual shimming) over a temperature range of -80 to 25 °C.  Although keeping up the pace I had set was difficult, for the first time at U. Akron I was making good progress towards finishing a degree.  One other thing which made this period enjoyable was that I had no further contact with “Kennedy.”

Binders of GPC data and NMR spectra collected in Collins’ lab by Dr. Lewis.

During the latter part of modeling work, in an attempt to figure out why cumyl methyl ether was not an efficient initiator with “holy grail”, I made an important discovery.  The NMR spectra afforded on reaction of cumyl methyl ether seemed to indicate an unusual decomposition reaction and in order to shed light on its mechanism the a related reaction (that of methanol with “holy grail”) was explored.  All of the modeling experiments were very difficult as moisture had to essentially non-existent. They also had to be initially conducted at low temperatures (ca. -80 °C) and were further complicated by the fact that milligram or sub-milligram quantities of reagents were always involved.  Since money was very tight and the solvent of choice (CD₂Cl₂) was expensive the use of stock solutions (which would have facilitated proper stoichiometry) was out of the question.  After numerous attempts to add exceedingly tiny amounts of methanol (in a controlled manner) to an NMR tube I (out of desperation) added in a huge excess.  I was just sick and tired of banging my head up against the wall spending up to 8 hours at a time trying to get the proper conditions that would placate Collins.  This act of defiance was fortuitous as something very unusual occurred.  When the amount of methanol was close to that of “holy grail” decomposition always resulted but this time when methanol was in a huge excess no decomposition happened.  I was amazed that hydrolytic cleavage of “holy grail” did not occur and seeing that the pKa of methanol is close to water I formulated what would be my very first invention, aqueous polymerization of IB.

*The end result of all my work prior to graduation was no less than 3 notebooks full of data (for Collins alone), >> 1,000 NMR spectra, and several journal articles and patents (not to mention a 300 page dissertation).