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:c Copyright 1990 American Chemical Society
Volume 9 , Number 12,December 1990
John K. Stille
Biographical Sketch Professor John K. Stille was horn May 8, 1930, in Tucson, Arizona. He received his bachelor's degree in 1 9 3 and master's degree in 1953, both from the Llniversitv of Arizona. He received his Ph.D. in 1957 from the University of Illinois under the supervision of the late Professor Marvel. In 1957, he joined the faculty a t the University of Iowa and became Professor in 1965. In 1977, Professor Stille joined the faculty at Colorado State University. In 1986 he was appoined University Distinguished Professor, one of seven such appointments a t Colorado State. Professor Stille had been a Visiting Professor at the Royal Institute in Stockholm (1969) and the University of Calilornia at Santa Cruz (1980). During his career, he directed 94 Ph.D. students and 97 postdoctoral fellows. He consulted for E. I. du Pont de Nemours & Co., Textile Fihers Department, since 1964 and was also a consultant for Syntex (USA) Inc. 0276-7333/90/2309-307$02.50/0
He won numerous awards, including the William H. Rauscher Memorial Lecturer (1974). the Gossett Lecturer (19i9), the Case Centennial Scholar (1980), the ACS Award in Pol.ymer Chemistry (1982), the 1989 American Chemical Society Colorado Section Award, and the Arthur C. Cope Scholars Award (1989). He served on the Advisory Board of Jnurnal of Polymw Science, the Editorial Boards of Advances in Polymer Science and Macromolecular Syntheses, and the Advisory Board o f Journal of Molecular Srience and served as an Associate Editor for Macromolecules between 196i and 1981. Professor Stille was an Associate Editor for the Journal of the American Chemical Society from 1982 through 1986 and was on the Advisory Board of Organometallics. He served as a frequent advisor to NASA. He authored over 270 publications, wrote two books. and contributed chapters to several books. He is survived by his wife Dolores and two sons, John Robert and James Kenneth. John Rohert, 31, is a faculty 0 1990 American Chemical Society
Organometallics 1990, 9, 3008-3010
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member in the chemistry department at Michigan State University, and James Kenneth, 29, is a chemical engineer at Syntex, Boulder, CO. Professor Stille's research accomplishments span a wide area of subjects, including mechanistic organometallic chemistry, catalysis, organic synthesis, and polymer chemistry. He carried out the seminal studies on the mechanism of oxidative-addition and reductive-elimination reactions of organic halides with palladium complexes, and his research in this area provides much of the current understanding of these processes. In addition, his careful studies on the stereochemistry of nucleophilic attack on palladium-complexed olefins, carbon monoxide insertion into metal-carbon bonds, and transmetalation were fundamental to the utilization of these processes in synthesis. In the area of catalysis, he developed the efficient palladium(0)-catalyzed carbonylation of organic halides, the palladium(I1)-catalyzedbis carboxylation of olefins, and the platinum-catalyzed asymmetric hydroformylation of olefins, with high enantiomeric excess and high branched to normal ratios. Perhaps his greatest contribution to catalysis was his development of the extremely general palladium-catalyzed coupling of organostannanes with organic halides and triflates. This mild C-C bond-forming
process is broadly tolerant of normally reactive functional groups and is being widely used by others for the synthesis of complex organic compounds. Stille himself led the way in his utilization of this chemistry in the total synthesis of' PGB,, coriolic acid, Lipoxin A, A9'l2)-capne1lene,amphinedine, and jatrophone. Professor Stille also directed an outstanding program in polymer chemistry, making major contributions in the areas of rigid-chain, thermally stable high-performance polymers including polyquinoxalines, polyphenylenes, and polyquinones. He carried out fundamental studies on the interaction of chain polymerization of vinyl monomers, through charge-transfer complexes, on Ziegler-Natta polymerization, and on the cross-linking of thermally stable aromatic polymers. He combined his interests in polymer chemistry and catalysis by tailor-making polymeric supports for transition-metal complex catalysts and was among the leaders in the field of polymer-supported catalysis. Such were the accomplishments of John Stille, a fine scientist and a fine man. He will be sorely missed. -Louis
S. Hegedus
L'ommuntcattons Synthesis and Structure of a [( 1,2-PhenyIenedioxy)boryi]iridium Hydride Complex: A Modet System for Studying Catalytic Hydroborationt Joseph R. Knorr and Joseph S. Merola" Department of Chemistry, Virginia Polytechnic Institute & State University, Blacksburg, Virginia 2406 1-02 12 Received May 14, 1990
Summary: Oxidative addition of the B-H bond in (1,2pheny1enedioxy)borane to Ir(COE)(PMe,),CI (COE = cyclooctene) produces mer-Ir(H)(BO,C,H,)(CI)(PMe,),, 1, which was characterized by single crystal X-ray diffraction. Compound 1 reacts with alkynes to form vinyliridium complexes and will catalyze the hydroboration of alkynes with (1,2-phenyIenedioxy)borane.
I
Hydroboration as a general class of reactions has found a prominent place among synthetic organic methodologies.'
While most hydroboration reactions do not require the use of metal catalysts, it has been shown that certain sluggish reactions may be accelerated by the use of a metal complex. Over the last several years, several examples of metal-promoted B-H addition across acetylenes and olefins have been reported.* It has been demonstrated that the use of a catalyst can direct the course of the hydroThis paper is dedicated to the memory of John K. Stille. L. Orgonoboranes in Organic Synthesis; Marcel Dekker: New York, 1973. (b) Brown, H. C. Tetrahedron 1981,37,3547. (2) (a) Herves, J. D.; Kreimendahl, C. W.; Marder, T. B.; Hawthorne, M. F. J. Am. Chem. SOC.1984,106,5757. (b) Sneddon,L. G. Pure Appl. Chem. 1987, 59, 837 and references therein. +
(1) (a) Cragg, G. M.
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Figure 1. ORTEP plot of 1. Important bond distances (A): Ir(l)-P(l),2.307 (2); Ir(l)-P(2), 2.351 (2); Ir(l)-P(3), 2.304 (2); Ir(l)-B(l), 2.023 (10); Ir(l)Cl(l), 2.546 (2). Important bond angles (deg): P(l)-Ir(l)-P(2), 97.7 (1); P(l)-Ir(l)-P(3), 163.6 (1); P(2)-Ir(l)-P(3), 97.7 (1); P(1)-Ir(l)-Cl(l), 85.9 (1); P(2)-Ir(l)-Cl(l), 94.8 (1); P(3)-Ir(l)-Cl(l), 87.4 (1); P(l)-Ir(l)-B(l), 94.8 (3); P(2)-Ir(l)-B(l), 92.7 (3); P(3)-Ir(l)-B(l), 89.9 (3); Cl(l)-Ir(l)B ( l ) , 172.3 (3).
boration reaction toward a different regiochemistry than the uncatalyzed r e a ~ t i o n . The ~ use of a catalyst to change 1990 American Chemical Society
