研究生专题报告暨高济宇有机化学前沿讲座

发布时间:2016-04-05浏览次数:2580

题  目:From Molecular Gyroscopes to Homeomorphic Isomerization: Molecules that Turn Themselves Inside-Out
报告人:John A. Gladysz教授
Department of Chemistry, Texas A&M University
时  间:2016年4月11号(星期一)上午10:30
地  点:仙林化学楼 H201报告厅
邀请人:强琚莉 副教授,王乐勇 教授
email:  gladysz@mail.chem.tamu.edu
Web: http://www.chem.tamu.edu/rgroup/gladysz/

    John A. Gladysz is a native of the Kalamazoo, Michigan area, and obtained his B.S. degree from the University of Michigan (1971) and his Ph.D degree from Stanford University (1974) with E. E. van Tamelen. He subsequently held appointments at UCLA (Assistant Professor, 1974-1982), the University of Utah (Associate Professor and Professor, 1982-1998), and the University of Erlangen-Nuremberg in Germany (Professor Ordinarius, 1998-2007). He then assumed the Dow Chair in Chemical Invention at Texas A&M University, where he is Distinguished Professor of Chemistry.
    Gladysz has been a fellow of the Alfred P. Sloan Foundation (1980-1984) and a Camille and Henry Dreyfus Teacher-Scholar Grant recipient (1980-1985). He received an Arthur C. Cope Scholar Award in 1988, the University of Utah Distinguished Research Award in 1992, the ACS Award in Organometallic Chemistry in 1994, a von Humboldt Foundation Research Award for Senior Scientists in 1995, the International Fluorous Technologies Award in 2007, the Texas A&M Distinguished Achievement Award in Research in 2013, and the Royal Society of Chemistry Award in Organometallic Chemistry in 2013. He was elected as a Fellow of the American Chemical Society in the inaugural year, 2009, and became a Fellow of the Royal Society of Chemistry in 2013.
    From June 1984 through July 2010, he served as the Associate Editor of Chemical Reviews. He then succeeded Dietmar Seyferth as the Editor in Chief of Organometallics, a position he held until January 2015.
    Gladysz has authored over 500 papers, book chapters, patents, and editorials, and his re¬search spans a wide range of problems in the general areas of synthetic and mechanistic organomet¬allic chemistry, and catalysis.
    On the personal side, he is married to Janet Blümel, a Professor of Chemistry at Texas A&M University who specializes in inorganic chemistry, supported catalysts, and solid state NMR spectroscopy. They live on the Crow's Nest Ranch, which consists of 137 acres (56 hectares) 4 miles east of College Station.
 
Abstract for Lecture:
    Children never cease to be fascinated by toy gyroscopes, which commonly consist of (1) a rotating axis and disk, and (2) two to four spokes that connect the termini of the axis. This talk will briefly describe the syntheses of the first molecules that duplicate the connectivity, symmetry (Dnh), and rotational ability of such gyroscopes. Complexes with trans R3P-MLn- PR3 linkages are first prepared, with R groups that terminate with a CH=CH2 moiety. Then alkene metathesis is used to construct a three-spoked cage molecule. The C=C units are hy¬drogenated to give gyroscope-like species. Yields are highest with rotators such as Fe(CO)3, which feature a three-fold symmetry axis, analogous to the phosphine ligands. However, re¬asonable yields can also be obtained with MLn = PtCl2, Rh(CO)Cl (square-planar geometry) and Re(CO)3X (octahedral geometry) .
    Certain complexes can be demetallated to yield dibridgehead diphosphines, which can exist as three diastereomers (phosphorus lone pairs in/in, out/out, or in/out). This provides a start¬ing point for another very interesting story. It has recently proved possible to show that these molecules rapidly turn themselves "inside-out" by a dynamic process that has only seldom been observed previously. These topologically novel equilibria interconvert what any chemist would regard as two configurational diastereomers by purely conformational processes.
 
References

[1] Stollenz, M.; Barbasiewicz, M.; Nawara-Hultzsch, A. J.; Fiedler, T.; Laddusaw, R.; Bhuvanesh, N.; Gladysz, J. A. Angew. Chem., Int. Ed. 2011, 50, 6647.
[2] Nawara-Hultzsch, A. J.; Stollenz, M.; Barbasiewicz, M.; Szafert, S.; Lis, T.; Hampel, F.; Bhuvan¬esh, N.; Gladysz, J. A. Chem. Eur. J. 2014, 20, 4617.
[3] Estrada, A. L.; Jia, T.; Bhuvanesh, N.; Blümel, J.; Gladysz, J. A. Eur. J. Inorg. Chem. 2015, 32, 5318.
[4] Stollenz, M.; Taher, D.; Bhuvanesh, N.; Reibenspies, J. H.; Baranová, Z.; Gladysz, J. A. Chem. Commun. 2015, 51, 16053.