D. Patrick Green -- PhD 1989

Scientific Career

Thesis Title
Studies of Phenyllithium, its Complexes in Donor Solvents, and its Role in the Lithium-Metalloid Exchange Reaction.
Research Summary Pat was the second person to work extensively in the organolithium-ate complex area, following up on Nancy Phillip's pioneering work. Pat did quantitative studies of PhLi in THF, and showed that TMEDA complexed PhLi but did not significantly activate it, whereas 12-crown-4 dramatically activated PhLi, but did not detectably complex with it. Both HMPA and PMDTA formed strong complexes with PhLi, and also greatly increased the reactivity.

Pat did extensive NMR and kinetic studies of the ate complexes formed between PhLi and PhI, Ph2Te and other metalloids in THF and THF-HMPA solutions. He showed that dibenzotellurophene formed a more stable ate complex with PhLi than did diphenyl telluride, and this set the stage for later work by Biggie Gudmundsson on stable selenium ate complexes.

Pat studied two more unusual ate complexes of the 12-electron type.
In connection with the ate complex work, Pat was the first person to observe J coupling between lithium and phosphorus in lithium reagents, and he initiated the group's very extensive studies on many lithium reagents and their interaction with HMPA and other strongly coordinating solvents which provided unprecedented details about solvation and ion pair structure. This includes work by Joe Borst. Bob Dykstra, Bill Sikorski, Jennifer Thopson, Biggie Gudmundsson, Klaus Kulicke, Aaron Sanders, Wayne Goldenberg and Kevin Jantzi.

  1. "The Lithium-Metalloid Exchange Reaction. NMR Studies of the Phenyllithium-Iodobenzene Exchange", H. J. Reich and D. P. Green, J. Am. Chem. Soc. 1989, 111, 3444. (Communication) PDF

  2. "Spectroscopic and Reactivity Studies of Lithium Reagent - HMPA Complexes", H. J. Reich and D. P. Green, J. Am. Chem. Soc. 1989, 111, 8729. (Communication)

  3. "The Lithium-Metalloid Exchange. Dynamics and Equilibrium in the Li/I and Li/Te Exchange in Tetrahydrofuran: Iodine Tellurium and Mercury Ate Complexes." H. J. Reich, D. P. Green and N. H. Phillips, J. Am. Chem. Soc. 1991, 113, 1414. (Communication) PDFl

  4. "Mechanism of the Lithium-Tellurium, Lithium Iodine and Lithium-Mercury Exchange Reactions: Hypervalent Tellurium and Iodine Ate Complexes", H. J. Reich, D. P. Green, N. H. Phillips and J. P. Borst, Phosphorus, Sulfur, Silicon, 1992, 67, 83. (Article) PDF

  5. "A Nuclear Magnetic Resonance Spectroscopic Technique for the Characterization of Lithium Ion Pair Structures in THF and THF/HMPA Solution", H. J. Reich, J. P. Borst, R. R. Dykstra, D. P. Green J. Am. Chem. Soc. 1993, 115, 8728-41. (Article).PDF

  6. "Aggregation and Reactivity of Phenyllithium Solutions," Hans J. Reich, D. Patrick Green, Marco A. Medina, Wayne S. Goldenberg, Birgir Ö. Gudmundsson, Robert R. Dykstra, and Nancy H. Phillips, J. Am. Chem. Soc. 1998, 120, 7201-7210. (Article)PDF Suppl.

  7. "The Role of Ate Complexes in the Lithium-Sulfur, Lithium-Selenium and Lithium-Tellurium Exchange Reactions," Hans J. Reich, Birgir Ö. Gudmundsson, D. Patrick Green, Martin J. Bevan, and Ieva L. Reich, Helv. Chim. Acta 2002, 85, 3748-3772. (Article) PDF

Current Position Resource Leader -Colloids and Dispersions, Corporate Research and Development
Dow Chemical Company

For comments, additions and corrections, send e-mail to Hans J. Reich