The Journal of
Physical Chemistry
Q Copyrighr. 1990. by r C Americon Chmieol Soeiery
VOLUME 94, NUMBER 20 OCTOBER 4,1990
KENNETH S. PITZER
Blography of Kenneth S. PHzer Kenneth Sanborn Pitzer was born to Russell K. and Flora Pitzer on January 6. 1914. in Pomona, California. Russell K. Pitzer was
a lawyer, who became involved with orange growing and later went into banking. As an alumnus of Pomona College. he was a leader in the development of the Claremont Colleges helping found Harvey Mudd. Claremont Men's College (currently Claremont McKenna College). and Pitzer College. Flora Sanborn Pitzer was at one time a mathematics teacher. She had a great positive influence in Ken's development as a child. Sadly, she died when he was only 13. 0022-3654/90/2094-7743$02SO/O
The family occupation of growing oranges provided work experience and diversion to Ken. He learned to drive a tractor at age 12. Occasionally, the Southern California weather would become dangerously cold for the oranges. Young Ken would then join in the work of setting out smudge pots in the groves in the middle ofthe night. Ken did his undergraduate work at California Institute of Technology in chemistry. His research career started in his freshman year with undergraduate research with A. A . Noyes on oxidation-reduction reactions of silver salts in solution. He credits the influence of Noyes at the very beginning of his stay at CalTech with ensuring that he chose chemistry over physics. He published his first independent paper as an undergraduate on the crystal structure of a perrhenate salt at the suggestion of Linus 0 I990 American Chemical Society
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Pauling using Pauling's X-ray apparatus. He graduated from CalTech in 1935, That same year Ken and Jean Mosher married. Jean was also raised in Pomona, and they had known each other since childhood. This marriage, now in its 55th year, has obviously been very happy. It has produced three children, Ann, Russell, and John. All three children are stable, productive members of society: Ann is the leader of a group of programmers at Scientific Associates, Inc.. in San Diego, Russell is Chairman of the Chemistry Department at The Ohio State University, and John works for the CIA in Washington as an economic analyst, recently estimating the Soviet economy. Ken and Jean have five grandchildren. After graduating from CalTech, Ken pursued graduate studies at the University of California, Berkeley. His thesis supervisor was Wendell Latimer. However, as always, Ken pursued an independent course in research. His most important research was the discovery of barriers to internal rotation which came about when he met J. D. Kemp. Kemp was puzzling over the interpretation of his low-temperature heat capacity data on ethane. Pitzer recognized that the room-temperature entropy of ethane from the heat capacity measurements could be reconciled with the spectroscopic data on ethane if it was assumed that a barrier to internal rotation of the methyl groups exists. Furthermore, the internal rotation barrier could be calculated through this reconciliation. This work was seminal with far-reaching implications. Torsional barriers have a wide-ranging impact throughout chemistry in determining the energetics of the various conformations available to organic molecules. Conformation is vital to the functioning of protein enzymes and plays a determining role in the course and kinetics of many chemical reactions. In 1937, two years after completing his undergraduate work, Ken received his Ph.D. and accepted a position as Instructor at Berkeley. During this period shortly before the Second World War, he obtained many important results in thermodynamics and internal rotation. H e also developed long-term research interests in electrolytic solutions and corresponding states. However, these topics flowered later. For the next decade, the main thrust of his research increasingly became the exploration of the implications of torsional barriers. First, molecules with less symmetry such as propane were studied. Here the methyl group on the central carbon interferes with the rotation of the other methyl group, and a method for taking this into account was developed. Then, using these molecules as prototypes, he began to calculate thermodynamic functions for most of the known hydrocarbons in the gas phase. To make this possible, a novel method was developed to estimate the vibrational contributions. Many molecules were treated. Indeed, the sheer volume of values of thermodynamic quantities produced by Ken and his co-workers during this period is staggering. I t is difficult to imagine assembling enough people for enough years to reproduce this work. The resulting data have been of enormous value and are still widely used. When the hydrocarbon work was extended to ring compounds, major implications of torsional barriers about ring conformations were revealed. For example, as one increases ring size starting with three-membered rings and going up to six-membered rings, the natural expectation would be that strain is a minimum at the five-membered ring since the C-C-C bond angle for the planar ring is very near the tetrahedral angle. However. the torsional repulsion between the methylene groups in the planar configuration can be reduced by distorting the molecule from planarity. Thus, cyclohexane in the chair form is the most stable saturated ring form. Indeed, the greater stability of the chair form of cyclohexane over the boat form is a consequence of the reduction of torsional strain in the chair by the complete staggering of the methylene groups. Ken discovered that the cyclopentane potential surface has a minimum when one of the carbon atoms pops up out of planarity relieving the methylene torsional strain and that the identity of the carbon atom which is out-of-plane rotates around the ring almost freely. a phenomenon which he dubbed "pseudorotation". In fact, cyclobutane is nonplanar at its potential minimum because of the torsional interaction between the methylene groups.
Ken rapidly rose academically, becoming Professor in 1945 even though his academic career was seriously affected by the war. During much of the Second World War, he worked on militar, research at the Maryland Research Laboratory and served as its Technical Director during 1943-1944. After the war, he returned to Berkeley and shortly became Assistant Dean of the College of Chemistry. Then in 1949 he began a two-year stint as Director of Research of the Atomic Energy Commission. When he returned to Berkeley, he became Dean of the College of Chemistrq. il position he held through 1960. Throughout the period from 1937 to 1956, he produced a tremendous outpouring of scientific papers primarily on thermodynamic properties of compounds. This output seemed scarcely affected by his deep involvement with the war effort or later with administration both of research and of academic matters. He also produced two books, Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds (1947) and Quantum Chemistry (1953). During the 1950s his research interests became more diverse, shifting toward spectroscopy, quantum chemistry, application of corresponding states, and the properties of metal-ammonia solutions. In particular. Ken's extension of the theory of corresponding states to nonspherical molecules by the invention of the acentric factor ha5 proved to be an extremely useful in predicting P-V-T and thermodynamic properties of fluids under a wide variety of conditions. His profound interest in thermodynamics culminated in the production with Leo Brewer of a completely revised edition of the classic text by Lewis and Randall, Thermodynamics, in 1961. The outstanding nature of his contributions to science throughout his career has been recognized through many honors and awards which are listed below. Ken has nurtured many graduate students and postdoctoral associates over his long career. A substantial fraction of these junior colleagues have gone into academics. More than a dozen of these have achieved substantial independent research reputations. Ken's most distinguished former student was George Pimente]. Ken has many, many academic grandchildren, greatgrandchildren, and great-great-grandchildren. Ken has always found time for relaxation, play, and fun. He enjoys travel and the outdoors, but his most serious avocation is sailing. Characteristically, he has pursued this interest with the same depth and passion with which he has always pursued science. Not only has he enthusiastically sailed whatever waters he is near from San Francisco Bay and Clear Lake to Chesapeake Bay and Galveston Bay, but he has designed and constructed several boats guided by a deep understanding of the physics of sailing. Ken takes special pride in being licensed by the Coast Guard as a boat designer and builder. Sometimes his designs were ahead of their time in their novelty. One of us (W.D.G.) recalls one such adventure vividly. The plan was to replace the cloth sail with an airfoil similar to an airplane wing. The idea was excellent, but, alas, high strength, lightweight materials such as Kevlar, Mylar, Dacron, epoxy resins, and Ti, AI, and Mg alloys either had not been invented or were not available even to one as resourceful as Ken. The airfoil constructed with the materials he could get really needed a stable platform such as a catamaran. but catamarans were then very rare. The airfoils were much too heavy, and the tests lasted only a few hours. When our day began, the breezes were very light and all worked well. Then the wind freshened a bit, resulting in the end of the first test within a few minutes. Subsequent tests were made, each ending more quickly. In total, the time spent in these tests turned out to be far shorter than the time required to get back to shore. The validity of the concept, however, has been proved. A similar airfoil sail mounted on the wide base of a catamaran was used to win the Americas Cup last summer in San Diego. In 1961 Kenneth Pitzer became the third president of Rice University. He took the job because he recognized that Rice was at a point where it could develop from a regional technical institute into a nationally recognized university, and he wished to lead and guide this transformation. As Houston was part of the old South, Rice was restricted to whites only. When Ken became President.
The Journal of Physical Chemistry, Vol. 94, No. 20, 1990 7745 Rice's Trustees successfully petitioned the local court to remove the whites-only clause from the charter. Simultaneously, the nature was officially changed from William Marsh Rice Institute to William Marsh Rice University reflecting Pitzer's vision of Rice as a great university. Rice experienced great growth during the seven years that Ken was president. Several new buildings were constructed, and several new academic programs were added. Many vigorous, creative new faculty members and administrators were recruited, transforming the campus mood to one where optimism and a sense of direction prevailed. Despite the many responsibilities of leadership, Ken maintained his own research program in chemistry. Feeling that it would be unfair to the student, he did not take graduate students during this period and worked only with postdoctoral associates. Some marvelously talented postdoctoral students joined him at Rice including Jurgen Hinze, Harry Hopkins, Jerry Kasper, Krishnan Sathianandan, and Stewart Strickler. His research during this period focused primarily on metal-ammonia solutions, matrix isolation, chemical lasers, bonding in noble gas compounds, and nuclear spin isomerization. I n 1968 after accomplishing much in setting a new direction for Rice, Ken became president of Stanford University. This step turned out much like jumping into boiling oil. In 1968, the firestorm of revolt against the Viet Nam War struck Stanford. Ken was thrust into the unenviable position of trying to lead the university through the chaos of student revolt. The values and personalities in conflict were irreconcilable, and the social fabric of the university was torn. Ken did his best to bring the university through this very difficult period, and Stanford managed to avoid the most extreme incidents which took place on the campuses of other major American universities. In 1971, undoubtedly with a sense of relief, Pitzer returned to Berkeley as Professor of Chemistry. Everyone involved with research knows that momentum is very
important. Nothing seems more difficult than starting over again in research. At Stanford, Ken had abandoned his research program, and at Berkeley at the age of 57, he restarted research. A measure of his success in this very difficult task is that he published 140 of the 334 papers listed below after returning to Berkeley. He started this new research career by rethinking theories of electrolytic solutions and expanding previous work started at Rice on nuclear spin conversion in solid methane. Then he developed the theoretical treatments of the effects of relativistic forces on chemical bonding in compounds involving the heavier elements. Recent years have seen an outpouring of new results, melding a longstanding interest in electrolytic solutions with an equally longstanding interest in equations of state and critical behavior to explore the exciting area of critical and supercritical ionic solution behavior. The USA often gives the impression of rootlessness. People move hither and thither across the country throughout their lives pursuing career goals. Ken and Jean Pitzer have always been willing to move to pursue a goal whether it is to serve the country near Washington or to develop a university like Rice or Stanford. However, ever since Ken chose Berkeley as the place to start his academic career, their roots have really remained there. They kept their home in Berkeley and their retreat home at Clear Lake throughout all their travels even though in fairness to Berkeley Ken had relinquished his professorship there. Their lives remind us that it is possible to reach out, to grow, to explore, and to lead without forgetting who we are and where our roots are. Fifty-five years of happy marriage with the hope of more to come and three adult, autonomous children are accomplishments with value equal to important advances in human knowledge and the development of a great university. A few rare, gifted, hard-working, lucky individuals have and do all these things.
Honors and Awards 1943 1949 1950 1951 1951 1958 1963 1965 1966 I969 I975 I976 I976 1978 1984 1984 I986 1986 1987 1988
American Chemical Society Award in Pure Chemistry Precision Scientific Co. Award in Petroleum Chemistry U S . Jr. Chamber of Commerce Award as One of the Ten Outstanding Young Men in the Nation Alumnus of the Year Award, University of California, Berkeley Guggenheim Fellowship Clayton Prize, Institution of Mechanical Engineers (London) Priestley Memorial Award (Dickinson College) Carlisle, PA Gilbert Newton Lewis Medal (California A.C.S.) Alumni Distinguished Service Award, California Institute of Technology, Pasadena, CA Priestley Medal, American Chemical Society National Medal of Science ( U S A . ) Gold Medal of the American Institute of Chemists Willard Gibbs Medal (Chicago Section, American Chemical Society) Centenary Lecturer, Chemical Society (Great Britain) Berkeley Citation (University of California) Robert A. Welch Award in Chemistry Honorary Fellow in the Indian Academy of Sciences Mack Award, The Ohio State University, Columbus, O H Pitzer Lecture, Department of Chemistry, University of California, Berkeley Rossini Lecture, 10th IUPAC Conference on Chemical Thermodynamics, Prague, Czechoslovakia
Robert F. Curl William D. Gwinn
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Argentic Salts in Acid Solution. I. The Oxidation and Reduction Reactions. J . Am. Chem. SOC.57, 1221 (1935). (With A. A. Noyes and J. L. Hoard.) Argentic Salts in Acid Solution. 11. The Oxidation-State of Argentic Salts. J . Am. Chem. SOC.57, 1229 (1935). (With A. A. Noyes and C. L. Dunn.) The Crystal Structure of Tetramminocadmium Perrhenate, Cd(NH,),(ReO,),. 2. Kristallogr., A 92, 131 (1935). Hindered Rotation of Methyl Groups in Ethane. J . Chem. Phys. 4, 749 (1936). (With J. D. Kemp.) The Entropy of Ethane and the Third Law of Thermodynamics. Hindered Rotation of Methyl Groups. J . Ani. Chem. SOC.59, 276 (1937). (With J . D. Kemp.) Thermodynamic Functions for Molecules Having Restricted Internal Rotations. J . Chem. Phys. 5 , 469 (1937). Thermodynamics of Gaseous Hydrocarbons: Ethane, Ethylene, Propane, Propylene, n-Butane, Isobutane, 1Butene, Cis and Trans 2-Butenes, Isobutene, and Neopentane (Tetramethylmethane). J . Chem. Phys. 5, 473 (1937). Errata: J . Chem. Phys. 5 , 752 (1937). The Heat Capacity and Entropy of Silver Nitrate from 15 to 300°K. The Heat and Free Energy of Solution in Water and Dilute Aqueous Ammonia. The Entropy of Silver Ammonia Complex Ion. J . Am. Chem. SOC.59. 1213 (1937). (With W. V. Smith and 0. L. I . Brown.) The Heats of Ionization of Water, Ammonium Hydroxide, Carbonic, Phosphoric, and Sulfuric Acids. The Variation of Ionization Constants with Temperature and the Entropy Change with Ionization. J . A m . Chem. SOC.59. 2365 (1937). Silver Oxide: Heat Capacity from 13 to 300"K, Entropy. Heat of Solution, and Heat and Free Energy of Formation. The Heat of Formation and Entropy of Silver Ion. J . Am. Chem. SOC.59, 2633 (1937). (With W. V. Smith.) Silver Chlorite: Its Heat Capacity from 15 to 300"K, Free Energy and Heat of Solution and Entropy. The Entropy of Chlorite Ion. J . Am. Chem. SOC. 59, 2640 (1937). (With W . V . Smith and W. M. Latimer.) Silver Chromate: Its Heat Capacity, Entropy and Free Energy of Formation. The Entropy and Free Energy of Formation of Chromate Ion. J . Am. Chem. SOC.59, 2642 (1937). (With W. V . Smith and W. M. Latimer.) The Heat Capacity of Diamond from 70 to 300'K. J . Chem. Phys. 6, 68 (1938). Restricted Internal Rotation in Hydrocarbons. J . A m . Chem. SOC.60, 1515 (1938). (With J. D. Kemp.) The Heat Capacities, Entropies, and Heats of Solution of Anhydrous Sodium Sulfate and of Sodium Sulfate Decahydrate. The Application of the Third Law of Thermodynamics to Hydrated Crystals. J . A m . Chem. SOC.60. 1310 (1938). (With L. V. Coulter.) The Heats of Solution of Cesium Perchlorate, Rubidium Perchlorate, Rubidium Chlorate, and Lead Phosphate. J . Am. Chem. SOC.60, 1828 ( 1 938). The Heat Capacity and Entropy of Barium Fluoride, Cesium Perchlorate and Lead Phosphate. J . Am. Chem. SOC.60, 1826 (1938). (With W . V . Smith and W. M. Latimer.) The Entropies of Aqueous Ions. J . A m . Chem. SOC.60. 1829 (1938). (With W . M. Latimer and W . V. Smith.) The Free Energy of Hydration of Gaseous Ions, and the Absolute Potential of the Normal Calomel Electrode. J . Chem. Phys. 7, 108 (1939). (With W. M. Latimer and C. M. Slansky.) The Symmetry Number and Thermodynamic Functions for Molecules Having Double Minimum Vibrations. J . Chem. Phys. 7, 251 (1939). Corresponding States for Perfect Liquids. J . Chem. Phys. 7. 583 ( 1 939). The Heat Capacities, Heats of Transition and Fusion, and 0022-3654/90/2094-7746$02.50/0
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Entropies of Ethylene Dichloride and Ethylene Dibromide. J . Am. Chem. SOC.62, 331 (1940). The Thermodynamics of n-heptane and 2,2,4-Trimethylpentane, Including Heat Capacities, Heats of Fusion and Vaporization and Entropies. J . Am. Chem. SOC.62, 1224 (1940). Book Reoiew. MacDougall, F. H . Thermodynamics and Chemistry. J . Phys. Chem. 44, 825 (1940). The Vibration Frequencies and Thermodynamic Functions of Long Chain Hydrocarbons. J . Chem. Phys. 8, 711 ( 1 940). Chemical Equilibria, Free Energies, and Heat Contents for Gaseous Hydrocarbons. Chem. Reu. 27, 39 (1940). The Entropies of Large Ions. The Heat Capacity, Entropy and Heat of Solution of Potassium Chloroplatinate, Tetramethylammonium Iodide and Uranyl Nitrate Hexahydrate. J . Am. Chem. SOC.62, 2845 (1940). (With W. M. Latimer and L. V. Coulter.) Scattering of 20' Neutrons in Ortho- and Parahydrogen. Phys. Rec. 58, 1003 (1940). (With L. W. Alvarez.) The Heat Capacity and Entropy of Silver Iodide and their Interpretation in Terms of Structure. J . Am. Chem. SOC. 63, 516 (1941). Thermodynamic Functions for Molecules with Internal Rotation. J . Chem. Phys. 9, 485 (1941). (With W. D. Gwinn.) Thermodynamic Properties of the Crystalline Forms of Silica. J . Am. Chem. SOC.63, 2348 (1941). (With M. A. Mosesman.) The Heat Capacity of Gaseous Paraffin Hydrocarbons, Including Experimental Values for n-Pentane and 2,2Dimethylbutane. J . Am. Chem. SOC.63, 2413 (1941). The Thermodynamics of Branched-Chain Paraffins. The Heat Capacity, Heat of Fusion and Vaporization, and Entropy of 2,3,4-Trimethylpentane. J . A m . Chem. SOC. 63, 2419 (1941). (With D. W. Scott.) Color and Bond Character. J . A m . Chem. SOC.63, 2472 (1941). (With Joel H . Hildebrand.) Nitromethane: The Heat Capacity of the Gas, the Vapor Density, the Barrier to Internal Rotation. J . Am. Chem. SOC.63, 3313 (1941). (With W. D. Gwinn.) Free Energies and Equilibria of Isomerization of the Butanes, Pentanes, Hexanes, and Heptanes. J . Res. Natl. Bur. Stand. 27, 529 (1941). R P 1440. (With F. D. Rossini and E. J . R. Prosen.) Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation. I . Rigid Frame with Attached Tops. J . Chem. Phys. 10, 428 (1942). (With W. D. Gwinn.) Internal Rotation in Molecules with Two or More Methyl Groups. J . Chem. Phys. 10, 605 (1942). The Thermodynamics and Molecular Structure of Benzene and Its Methyl Derivatives. J . A m . Chem. SOC.65, 803 (1943). (With Donald W. Scott.) Thermodynamics of Styrene (Phenylethylene), Including Equilibrium of Formation from Ethyl Benzene. J . Am. Chem. SOC.65, 1246 (1943). (With L. Guttman and E. F. Westrum, Jr.) The Molecu!ar Structure and Thermodynamics of Propane. The Vibration Frequencies, Barrier to Internal Rotation, Entropy, and Heat Capacity. J . Chem. Phys. 12, 310 (1944). Thermodynamics of Gaseous Paraffins. Specific Heat and Related Properties. Ind. Eng. Chem. 36, 829 (1944). trans-2-Butene. The Heat Capacity, Heats of Fusion and Vaporization, and Vapor Pressure. The Entropy and Barrier to Internal Rotation. J . Am. Chem. SOC.67, 324 (1945). (With L. Guttman.) Heats, Free Energies, and Equilibrium Constants of Some Reactions Involving O,, H,, H,O, C , CO, CO,, and CH,.
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J . Res. Natl. Bur. Stand. 34, 143 (1949, R P 1634. (With D.D. Wagman, J. E. Kilpatrick, W. J. Taylor, and F. D. Rossini.) Free Energies and Equilibria of Isomerization of the 18 Octanes. J . Res. Null. Bur. Stand. 34, 255 ( I 945), R P 1641. (With E. J. Prosen and F. D. Rossini.) Heats and Free Energies of Formation of the Paraffin Hydrocarbons, in the Gaseous State, to 1500'K. J . Res. Natl. Bur. Stand. 34,403 (1945). (With E. J. Prosen and F. D. Rossini.) Strain Energies of Cyclic Hydrocarbons. Science 101,672 (1945). Book Review. Palmer, W. G., Valency, Classical and Modern. J. Phys. Chem. 49, 166 (1945). Electron Deficient Molecules. I. The Principles of Hydroboron Structures. J . Am. Chem. SOC.67, 1126 (1945). The Heat Capacity and the Entropy of Hydrated Lanthanum Magnesium Nitrate. J . Am. Chem. SOC.67, 1444 (1945). (With F. J. Fornoff and W. M. Latimer.) Energy Levels and Thermodynamic Functions for Molecules and Internal Rotation. 11. Unsymmetrical Tops Attached to a Rigid Frame. J . Chem. Phys. 14, 239 (1946). The Thermodynamics of 2,2-Dimethylbutane, Including the Heat Capacity, Heats of Transitions, Fusion and Vaporization and the Entropy. J . Am. Chem. SOC.68, 1066 (1946). (With J . E. Kilpatrick.) Bending Force Constants for Halogenated Ethylenes. J . Chem. Phys. 14, 586 (1946). (With N. K. Freeman.) Electron Deficient Molecules. 11. Aluminum Alkyls. J . Am. Chem. SOC.68,2204 (1946). (With H. S. Gutowsky.) The Heat Capacity, Heats of Fusion and Vaporization, Vapor Pressure, Entropy, Vibration Frequencies and Barrier to Internal Rotation of Styrene. J . Am. Chem. SOC.68, 2209 (1946). (With L. Guttman and E. F. Westrum, Jr.) The Thermodynamics of Styrene and its Methyl Derivatives. J . Am. Chem. SOC.68, 2213 (1946). (With C. W. Beckett .) Heats, Equilibrium Constants and Free Energies of Formation of the Acetylene Hydrocarbons through the Pentynes to 1500OK. J . Res. Natl. Bur. Stand. 35,467 (1945), R P 1682. (With D. D. Wagman, J. E. Kilpatrick, and F. D. Rossini.) Heats, Equilibrium Constants, and Free Energies of Formation of the Monoolefin Hydrocarbons. J . Res. Natl. Bur. Stand. 36, 559 (1946), R P 1722. (With J. E. Kilpatrick, E. J . Prosen, and F. D. Rossini.) Heats, Equilibrium Constants and Free Energies of Formation of Alkylbenzenes. J . Res. Natl. Bur. Stand. 37, 95 (1946), R P 1732. (With W. J. Taylor, D. D. Wagman, M. G. Williams, and F. D. Rossini.) Heat Content, Free Energy Function, Entropy and Heat Capacity of Ethylene, Propylene and the Four Butenes to 1500OK. J . Res. Natl. Bur. Stand. 37, 163 (1946), R P 1738. (With J. E. Kilpatrick.) The Entropies and Related Properties of Branched Paraffin Hydrocarbons. Chem. Rev. 39,435 (1946). (With J. E. Kilpatrick.) The Heat Capacity of Gaseous Cyclopentane, Cyclohexane and Methylcyclohexane. J . Am. Chem. SOC.68, 2537 (1946). (With R. Spitzer.) Pancake Effect in Gas Clouds. OSRR No. 1 176. Publication Board 15620. (With W . M. Latimer and W . D. Gwinn.) Vibrational Frequencies of Semi-rigid Molecules: A General Method and Values for Ethylbenzene. J . Res. Natl. Bur. Stand. 38, 1 (1947), R P 1758. (With W. J. Taylor.) Normal Coordinate Analysis of the Vibrational Frequencies of Ethylene, Propylene, cis-2-Butene, trans-2-Butene, and Isobutene. J . Res. Natl. Bur. Stand. 38, 191 (1947), R P 1768. (With J. E. Kilpatrick.) Electron Deficient Molecules. 111. The Entropy of Diborane. J . Am. Chem. SOC.69, 184 (1947).
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Tautomerism in Cyclohexane Derivatives: Reassignment of Configuration of the I ,3-Dimethylcyclohexanes. J . Am.
Chem. SOC.69, 977 (1947). (With C. W. Beckett.) Relabeling of the Cis and Trans Isomers of 1,3-Dimethylcyclohexane. Science 105, 647 (1947). (With F. D. Rossini.) 69. The Nature of the Hydrogen Bond in KHF,. J . Chem. Phys. 15, 526 (1947). (With E. F. Westrum, Jr.) 70. The Thermodynamics and Molecular Structure of Cyclopentane. J . Am. Chem. SOC.69, 2483 (1947). (With J . E. Kilpatrick and R. Spitzer.) 71. The Thermodynamic Properties and Molecular Structure of Cyclohexane, Methylcyclohexane, Ethylcyclohexane and the Seven Dimethylcyclohexanes. J . Am. Chem. SOC.69, 2488 (1947). (With C. W. Beckett and R. Spitzer.) 72. Heats, Equilibrium Constants, and Free Energies of Formation of the Alkylcyclopentanes and Alkylcyclohexanes. J . Res. Narl. Bur. Stand. 39, 523 (1947), R P 1845. (With J. E. Kilpatrick, H. G. Werner, C. W . Beckett, and F. D. Rossini.) 73. Strains in Methyl Amines and Hydrocarbons. J . Am. Chem. SOC.70, 1261 (1948). (With R. Spitzer.) 74. The Infra-Red Spectrum and Structure of Aluminum Trimethyl. J . Chem. Phys. 16, 552 (1 948). (With R. K. Sheline.) 75. Gas Heat Capacity and Internal Rotation in 1,2-Dichloroethane and 1,2-Dibromoethane. J . Chem. Phys. 16, 303 (1948). (With W. D. Gwinn.) 76. Repulsive Forces in Relation to Bond Energies, Distances and Other Properties. J . Am. Chem. SOC.70,2140 (1948). 77. The Thermodynamic Properties and Molecular Structure of Cyclopentene and Cyclohexene. J . Am. Chem. SOC.70, 4227 (1948). (With C. W. Beckett and N. K. Freeman.) 78. Heats, Equilibrium Constants, and Free Energies of Formation of the C3 to Cs Diolefins, Styrene, and the Methylstyrenes. J . Res. Natl. Bur. Srand. 42, 225 (l949), R P 1964. (With J. E. Kilpatrick, C. W. Beckett, E. J. Prosen, and F. D. Rossini.) 79. Heats, Equilibrium Constants, and Free Energies of Formation of Cyclopentene and Cyclohexene. J . Res. Natl. Bur. Stand. 42, 379 (l949), R P 1976. (With M. B. Epstein and F. D. Rossini.) 80. Thermodynamics of the System KHF2-KF-HF, Including Heat Capacities and Entropies of KHFz and KF. The Nature of the Hydrogen Bond in KHF2. J . Am. Chem. SOC.71, 1940 (1949). (With E. F. Westrum, Jr.) 8 1 . Thermodynamics and Vibrational Spectrum of Acetaldehyde. J . Am. Chem. SOC.71,2842 (1949). (With W. Weltner, Jr.) 82. Solutions of Diborane in Ammonia. J . Am. Chem. SOC. 71, 2783 (1949). (With G.W. Rathjens, Jr.) 8 3 . Heats, Equilibrium Constants, and Free Energies of Formation of the Dimethylcyclopentanes. J . Res. Natl. Bur. Stand. 43, 245 (1949), R P 2026. (With M. B. Epstein, G. M. Barrow, and F. D. Rossini.) 84. The Ultraviolet Absorption and Luminescence of Decaborane. J . Chem. Phys. 17, 882 (1949). (With G. C. Pimentel.) 85. The Infra-Red and Raman Spectra and the Thermodynamic Properties of Diborane. J . Chem. Phys. 17, 1007 (1949). (With A. N. Webb and J . T. Neu.) 86. Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation. 111. Compound Rotation. J . Chem. Phys. 17, 1064 (1949). (With J. E. Kilpatrick.) 87. Thermodynamic Properties of Some Sulfur Compounds. fnd. Eng. Chem. 41, 2737 (1949). (With G . M. Barrow.) 88. Carbon Isotope Effect on Reaction Rates. J . Chem. Phys. 17, 1341 (1949). 89. The Infrared Spectra and Structures of the Iron Carbonyls. J . Am. Chem. SOC.72, 1107 (1950). (With R. K. Sheline.) 90. 1. The Infra-Red Spectrum of Tetramethyl Lead and the Force Constants of M(CH3)4Type Molecules. J . Chem. Phys. 18, 595 (1950). (With R. K. Sheline.) 68.
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lymerization Equilibria in the Vapor, and Potential Barrier to Internal Rotation. J . Am. Chem. SOC.73,2606 (1951). (With W. Weltner, Jr.) The Role of Chemistry in the Development of Atomic Energy. Chem. Eng. News 29,4836 (1951). (With S. G. English.) Potential Energies for Rotation About Single Bonds. Faraday Discuss. Chem. SOC.No. 10,66 (1951). What's Wrong with Our Atomic Energy Program. Nucleonics 10, I O (1952). Book Reuiew. Taylor, H. S.; Jones, D. B.; Glasstone, S. A Treatise on Physical Chemistry, 3rd ed.; D. Van Nostrand: New York, 1951. J . Am. Chem. SOC.74,2128
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262. Thermodynamics of Sodium Chloride Solutions in Steam. J. Phys. Chem, 87, 1 120 ( I 983 i . 263. Thermodynamics of Saturated Aqueous Solutions Including Mixtures of NaCI, KCI, and CsCI. J. Solution Chem, 12, I7 I ( I 983). (With M , Concei@o P. de Lima.) 264. Thermodynamics of Saturated Electrolyte Mixtures of NaCl with Na2S0, and with MgCI,. J . Solution Chem. 12, 187 (1983). (With M. Concei$io P. de Lima.) 265. Thermodynamics of Aqueous Calcium Chloride. J . Solution Chem. 12, 201 (1983). (With Ramesh C . Phutela.) 266. Thermodynamics of the Unsymmetrical Mixed Electrolyte HCI-LaC13. J . Phys. Chem. 87, 2365 (1983). (With Rabindra N. Roy, James J . Gibbons, and J . Christopher Peiper.) 267. Thermodynamics of Unsymmetrical Electrolyte Mixtures. Enthalpy and Heat Capacity. J . Phys. Chem. 87, 2360 (1983). 268. Comparison of Experimental Values of To2,CPo2,and CVo2 for Aqueous NaCl with Predictions Using the Born Equation at Temperatures from 300 to 573.15 K at 17.7 MPa. J . Phys. Chem. 87, 3297-3300 (1983). (With Robert H. Wood, David Smith-Magowan, and P. S. Z. Rogers.) 269. Dielectric constant of water at very high temperature and pressure. Proc. Natl. Acad. Sci. U.S.A. 80, 4575-4576 ( 1 983). 270. Relativistic Molecular Structure Calculations Including CI for Several Low Lying States of SnO. Chem. Phys. Lett. 100, 273-276 (1983). (With K. Balasubramanian.) 271. The ground and excited states of PtH and PtH+ by relativistic ab initio electronic structure calculations: A model study for hydrogen chemisorption on platinum surfaces and related photoemission properties. J . Chem. Phys. 79, 3851-58 (1983). (With S. W . Wang.) 272. Relativistic Configuration Interaction Calculations for Several Low-Lying States of PbO: Comparison with Chemiluminescent Spectra. J . Phys. Chem. 87, 4857 (1983). (With K. Balasubramanian.) 273. Ab Initio potential energy curves for the low-lying electronic states of the argon excimer. J . Chem. Phys. 79, 6145-49 (1983). (With J . H. Yates, W. C. Ermler, N. W. Winter, P. A. Christiansen, and Y. S. Lee.) 214. Thermodynamics of Aqueous Sodium Chloride to 823 K and 1 kilobar (100 MPa). Proc. Natl. Acad. Sci. U.S.A. 80, 7689-7693 (1983). (With Yi-Gui Li.) 275. Relativistic Quantum Calculations of Low-Lying States of SnH: Comparisons with the Electronic Spectra of SnH and with the Properties of PbH. J . Mol. Spectrosc. 103, 105-12 (1984). (With K . Balasubramanian.) 276. Relativistic Calculations of Dissociation Energies and Related Properties. fnt. J . Quantum Chem. 25, 131-48 ( I 984). Lecture at Symposium on Relativistic Effects in Quantum Chemistry at A b Akademi, Finland, June 21-23, 1982. 277. Critical phenomena and thermodynamics of dilute aqueous sodium chloride to 823 . Proc. Natl. Acad. Sci. U.S.A. 81, 1268-71 (1984). (With Yi-gui Li.) 278. The Thermodynamics of Aqueous Carbonate Solutions. 11. Mixtures of Potassium Carbonate, Bicarbonate, and Chloride. J . Chem. Thermodyn. 16, 303-15 (1984). (With Rabindra N . Roy, James J. Gibbons, Rick Williams, Lehman Godwin, Gigi Baker, and John M. Simonson.) 279. Thermodynamic Properties of Aqueous Sodium Chloride Solutions. J . Phys. Chem. Ref Data 13, 1-102 (1984). (With J. C. Peiper and R. H . Busey.) 280. Relativistic Quantum Calculations of Low-Lying States of Lead Hydride. Comparison with Experimental Spectra. J . Phys. Chem. 88, 1146-8 (1984). (With K. Balasubramanian.) 281. Ion Pairing in a System Continuously Miscible from the Fused Salt to Dilute Solution. J . Am. Chem. Soc. 106, 1973-7 (1984). (With John M. Simonson.) 282 Ionic Fluids. J . Phys. Chem. 88, 2689-97 (1984).
7752 The Journal of Physical Chemistry, Vol. 94. No. 20. 1990 283. Critical Point and Vapor Pressure of Ionic Fluids Including NaCl and KCI. Chem. Phys. Lett. 105, 484-9 (1984). 284. Electron Structure of Molecules with Very Heavy Atoms Using Effective Core Potentials. N A T O Adc. Sci. Insrr. Ser., Ser. B 87, 403, Lecture at Symposium on Relativistic Effects in Quantum Chemistry at Vancouver, B.C., Aug 1981. 285. Gilbert N . Lewis and the Thermodynamics of Strong Electrolytes. J . Chem. Educ. 61, 104-7 (1984). 286. Biographical Memoirs of William Francis Giauque, American Philosophical Society Year Book 1983, p 398. 287. Biographical Memoirs of Joel Henry Hildebrand, American Philosophical Society Year Book 1983, p 408. 288. Thermodynamics of Condensed Ionic Systems. NATO Adv. Sci. Inst. Ser., Ser. C 130, 165-96 (1984). 289. A Consideration of Pitzer's Equations for Activity and Osmotic Coefficients in Mixed Electrolytes. J . Chem. Soc., Faraday Trans. I 80, 3451-4 (1984). 290. Thermodynamics of Aqueous Magnesium and Calcium Bicarbonates and Mixtures with Chloride. J . Chem. Eng. Data 30, 14-17 (1985). (With Joyce Olsen, John M. Simonson, Rabindra N . Roy, James J. Gibbons, and LeAnn Rowe.) 291. Critical Point and Phase Separation for an Ionic System. J . Phys. Chem. 89, 1854-5 (1985). (With M. Conceicao P. de Lima and Donald R. Schreiber.) 292. Relativistic Effects in Chemical Systems. Annu. Rev. Phys. Chem. 36, 407-32 (1985). (With Phillip A. Christiansen and Walter c. Ermler.) 293. Phase Relations and Adiabats in Boiling Seafloor Geothermal Systems. Earth Planet. Sci. Lett. 75, 327-38 (1985). (With James L. Bischoff.) 294. Heat Capacity and Other Thermodynamic Properties of Aqueous Magnesium Sulfate to 473 K. J . Phys. Chem. 90, 895-901 (1986). (With Ramesh C. Phutela.) 295. Large-Scale Fluctuations and the Critical Behavior of Dilute NaCl in H 2 0 . J . Phys. Chem. 90, 1402-4 (1986). 296. Thermodynamics of Multicomponent, Miscible, Ionic Systems: Theory and Equations. J . Phys. Chem. 90, 3005-9 (1986). (With John M. Simonson.) 291. Thermodynamics of Multicomponent, Miscible, Ionic Systems: The System LiN03-KN03-H20.J . Phys. Chem. 90, 3009-13 (1986). (With John M. Simonson.) 298. Densities and Apparent Molar Volumes of Aqueous Magnesium Sulfate and Sodium Sulfate to 473 K and 100 bar. J . Chem. Eng. Data 31, 320 (1986). (With Ramesh C. Phutela.) 299. Thermodynamics of NaCl in steam. Geochim. Cosmochim. Acta 50, 1445-54 (1986). (With Roberto T. Pabalan.) 300. Thermodynamic Properties of Aqueous NaCl from 273 to 823 K with Estimates for Higher Temperatures. I n Proceedings of the 10th International Conference on The Properties o f s t e a m ; Sytchev, V. V., Aleksandrov, A. A,, Eds.; Mir Publishers: Moscow, 1986; Vol. 2, pp 91-1 20. (conference held 3-7 Sept, 1984). 301. The system NaCI-H20: Relations of vapor-liquid near the critical temperature of water and of vapor-liquid-halite from 300" to 500 "C. Geochim. Cosmochim. Acta 50, 1437-44 (1986). (With James L. Bischoff and Robert J . Rosenba uer. ) 302. Thermodynamics of Electrolyte Mixtures. Enthalpy and the Effect of Temperature on the Activity Coefficient. J . Solution Chem. 15, 649-62 (1986). (With Ramesh C. Phutela.) 303. Theoretial considerations of solubility with emphasis on mixed aqueous electrolytes. Pure Appl. Chem. 58, 1599-1 6 I O (1986). 304. Thermodynamic properties of ionic fluids over wide ranges of temperature. Pure Appl. Chem. 59, 1-6 (1987). 305. Thermodynamics of Aqueous Magnesium Chloride, Calcium Chloride, and Strontium Chloride at Elevated Temperatures. J . Chem. Eng. Data 32, 76-80 (1987). (With Ramesh C. Phutela and Preet P. S. Saluja.)
306. High-temperature thermodynamic properties of several 1 : 1 electrolytes. Can. J . Chem. 64, 1328-35 (1986). (With Preet P. S. Saluja and Ramesh C. Phutela.) 307. Relativistic Quantum Chemistry, A b Initio Methods in Quantum Chemistry-I; Lawley, K. P., Ed.; Wiley: New York, 1987; pp 287-319. (With K. Balasubramanian.) 308. The Dipositive Dimeric Ion Hg22t: A Theoretical Study. J . Phys. Chem. 91, 1084-7 (1987). (With Randy P. Neisler.) 309. Critical Behavior of Dilute NaCl in H 2 0 . Chem. Phys. Lett. 134, 60-3 (1987). (With James L. Bischoff and Robert J . Rosenbauer.) 310. The restricted primitive model for ionic fluids. Properties of the vapour and the critical region. Mol. Phys. 60, 1067-78 ( 1 987). (With Donald R. Schreiber.) 31 I . Thermodynamics of NaOH(aq) in Hydrothermal Solutions. Geochim. Cosmochim. Acta 51, 829-37 (1987). (With Roberto T. Pabalan.) 312. Electrical Conductivity, Viscosity, and Density of a TwoComponent Ionic System at Its Critical Point. J . Phys. Chem. 91,4087-4091 (1987). (With Donald R. Schreiber and M. Conceicao P. De Lima.) 313. Thermodynamics of Concentrated Electrolyte Mixtures and the Prediction of Mineral Solubilities to High Temperatures for Mixtures in the System Na-K-Mg-CI-S04-OH-H20. Geochim. Cosmochim. Acta 51,2429-2443 (1987). (With Roberto T. Pabalan.) 314. A Thermodynamic Model for Aqueous Solutions of Liquid-Like Density. I n Reviews in Mineralogy; Vol. 17. Chapter 4; Carmichael, I . S. E., Eugster, H . P., Eds.; Mineralogical Society of America: Washington, DC, 1987; pp 97-142. 315. Of Physical Chemistry and Other Activities. Annu. Rec;. Phys. Chem. 38, 1-25 (1987). 316. Improving Equation-of-State Accuracy in the Critical Region; Equations for Carbon Dioxide and Neopentane as Examples. Fluid Phase Equilib. 41, 1-17 (1988). (With Donald R. Schreiber.) 317. Apparent Molar Heat Capacity and Other Thermodynamic Properties of Aqueous KCI Solutions to High Temperatures and Pressures. J. Chem. Eng. Data 33, 354-362 (1988). (With Roberto T. Pabalan.) 318. Thermodynamics of Electrolyte Mixtures. Activity and Osmotic Coefficients Consistent with the Higher-Order Limiting Law for Symmetrical Mixing. J . Solution Chem. 17, 909-924 (1988). (With Jia-zhen Yang.) 319. Near-Critical NaCI-H20: An Equation of State and Discussion of Anomalous Properties. Int. J . Thermophys. 9, 635-648 (1988). (With John C. Tanger IV.) 320. Selected Equation of State in the Acentric Factor System. Int. J . Thermophys. 9,965-974 (1988). (With Donald R. Schreiber.) 321. Thermodynamics of Aqueous Uranyl Sulfate to 559 K. J . Solution Chem. 18, 189-198 (1989). (With Jia-zhen Yang.) 322. Heat Capacity and Other Thermodynamic Properties of Na2S04(aq)in Hydrothermal Solutions and the Solubilities of Sodium Sulfate Minerals in the System Na-CI-S04-OH - H 2 0 to 300 "C. Geochim. Cosmochim. Acta 52, 2393-2404 (1988). (With Roberto T. Pabalan.) 323 An Ionic System with Critical Point at 44 "C. J . A m . Chem. Soc. 110, 8723-8724 (1988). (With Rajiv R. Singh.) 3 24 Liquid-Vapor Relations for the System NaCI-H20: Summary of the P-T-x Surface from 300" to 500 "C. A m . J . Sci. 289, 217-248 (1989). (With James L. Bischoff.) 325 Some Interesting Properties of Vapor-Liquid or LiquidLiquid Coexistence Curves for Ionic and Non-Ionic Fluids. Thermochim. Acta 139, 25-32 (1989). 326 The Application of the Ion-Interaction Model to Multicomponent 1 - 1 Type Electrolytes in Mixed Solvents. J . Solution Chem. 18, 201-210 (1989). (With Jia-zhen Yang.)
J . Phys. Chem. 1990, 94, 7153-7759 327. Fluids, Both Ionic and Nonionic, Over Wide Ranges of Temperature and Composition. Pure Appl. Chem. 61, 979-988 (1989); also J . Chem. Thermodyn. 21, 1-17 ( 1 989).
328. Relationships in the Approach to Criticality in Fluids, Including Systematic Differences Between Vapor-Liquid and Liquid-Liquid Systems. J . Chem. Phys. 90,5742-5748 (1989). (With Rajiv R. Singh.) 329. Critical Exponents for the Coexistence Curves for NaCI-HzO Near the Critical Temperature of HzO. Reply to Comment by A. H. Harvey and J. M. H. Levelt Sengers. Chem. Phys. Lett. 156, 418-419 (1989). (With John C. Tanger IV.) 330. Calculation of the Thermodynamic Properties of Aqueous Electrolytes to 1000 O C and 5000 bar from a Semicontinuum Model for Ion Hydration. J . Phys. Chem. 93, 4941-4951 (1989). (With John C. Tanger IV.) 33 I . Thermodynamics of NaCI-H,O; a New Equation of State for the Near-Critical Region and Comparisons with Other Equations for Adjoining Regions. Geochim. Cosmochim. Acta 53, 973-987 (1989). (With John C. Tanger IV.)
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332. Equation of State in the Acentric Factor System. Fluid Phase Equilibr. 46, 113-130 (1989). (With Donald R. Schreiber.) 333. Volume Changes for Mixing the Major Sea Salts: Equations Valid to Ionic Strength 3.0 and Temperature to 95 OC. J . Solution Chem. 18, 1007 (1989). (With L. M. Connaughton and F. J. Millero.) 334. Calculation of the Ionization Constant of H 2 0 to 2,273 K and 500 MPa. AIChE J . 35, 1631-1638 (1989). (With John C. Tanger IV.)
Books Quantum Chemistry;Prentice-Hall: New York, 1953; 492 pp. Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds; Published for the American Petroleum Institute, Carnegie Press, Pittsburgh, Carnegie Institute of Technology, Pittsburgh, 1947; 2nd ed., 1953. With L. Brewer. Revised edition of Lewis and Randall's Thermodynamics; McGraw-Hill Book Co.: New York, 1961.
Ab Initio Study of Bondlng Trends. 4. The 22-Electron A=B=C Series: Possible New Anions down to NCBe and Possible New Cations up to FNFS++ Pekka Pyykko* and Yongfang Zhaot Department of Chemistry, University of Helsinki, Et. Hesperiankatu 4 , 001 00 Helsinki, Finland (Received: September 6, 1989; In Final Form: February 22, 1990)
The 22-electron double-bonded A=B=C" systems with net charges -4 I n I 4 are screened for possible new species near known "stability islands". Initial HF/6-31G* results are screened further with a 6-31 lG* basis and MPn or CISD methods for the possible gas-phase species. The bond lengths of C22-and NCNZ- in a simple crystal field model differ by only a few picometers from the free-ion values, indicating that the anion calculations are meaningful. The calculated bond lengths and vibrational frequencies reproduce the experimental trends down to NBN3-. The possible new species include NCBe or NBCe near the known CCCe, NCC' or OBC' near the known NBNf, and OBN2- near the known NCN". The calculated geometry for NNC2- is close to that observed for the nitrile imine R-NNC-R'. The cations 0OO2+and FNF3+of ref 2 are still predicted to be locally stable.
Introduction
The purpose of the present series is to study simple isoelectronic systems with particularly stable bonding, by systematically varying the nuclear charges, sometimes to radically different values, in order to study bonding trends and to identify any possible new species outside the known "stability islands". In the parts 1-3' we considered the 14-electron A=B, the 22-electron symmetrical A=B=A, and the 32-electron AB3(D3,,) systems, respectively. The object of the present, part 4, is to generalize the 22-electron (1 6 valence electron) triatomic problem to the asymmetrical, A=B< case. Improved results on the new symmetrical species 0002+ and FNF3+are also reported. Results on ABC species containing S2 or P3 are published elsewhere. At the level of writing new structural formulas, this line has some rather respectable ancestors. Langmuir (ref 4, Table I) quoted in 1919 21 "isosteric" series (of which the present AB, ABC, and AB3 ones are numbers 8, IO, and 1 1, respectively)! His four ABC examples were OCO, NNO, N3-, and "CNO-". In 1958 Cordes,s who prepared Mg2C3and presented chemical evidence that it contains a CJ4- group, also mentioned the then existing 'Dedicated to Professor Kenneth S. Pitzer on his 75th birthday. 'On leave of absence from the Institute of Atomic and Molecular Physics. Jilin University, 130023 Changchun, PRC.
0022-3654/90/2094-7753$02.50/0
NCN2-, NCO-, NCF, and O N O + and the possible NCC3-, CC02-, NNF+, and OO02+. In 1961 Goubeau and Anselment6 predicted, and subsequently synthesized, several NBN3- salts, as a sequel to NCN2- and NNN-. The ketenide group, OCC2-, is known as a ligand in transition-metal complexes.' Some further data on heteroorganic compounds related to the present fragments are given below. The mononegative species are labeled "pseudohalogenides",8 the dinegative ones "pseudo~halcogenides",~ etc. ( I ) (a) Pyykko, P. Mol. Pfiys. 1989,67,871-878. (b) Pyykko, P. Cfiem. Pfiys. Lett. 1989,156,337-340. (c) Hotokka, M.; Pyykko, P. Cfiem. Pfiys. Lett. 1989,157, 415-418. (2) Pyykko, P. Cfiem. Pfiys. Lett. 1989,162,349-354. (3) Pyykko, P.; Zhao, Y.-F.Mol. Pfiys., in press. (4) Langmuir, I. J . Am. Cfiem. SOC.1919,4/, 1543-1559. (5) Cordes, J. F. Z. Noturforscfi. 1958,136, 622-623. (6) Goubeau, J.; Anselment, W. Z. Anorg. Allg. Chem. 1961, 310, 248-260. (7) (a) Blues, E. T.; Bryce-Smith, D.; Karimpour, H. Cfiem. Commun. 1979, 1043-1045. (b) Kreissl, F. R.; Sieber, W.; Wolfgruber, M. Z. Narurforscfi. 1982,37b, 1485-1486. (c) Neithamer, D. R.; La Pointe, R. E.; Wheeler, R. A,; Richeson, D. S.;Van Duyne, G. D.; Wolczanski, P. T. J . Am. Cfiem.SOC.1989,1 I I , 9056-9072. (8) Birckenbach, L.; Kellerman, K. Ber. Dtscfi. Cfiem. Ges. 1925, 58, 786-794. (9) Kohler, H. Z. Cfiem. 1971,11, 385.
0 1990 American Chemical Society
