Dr. Richard L. Keiter
Distinguished Professor Emeritus
Eastern Illinois University
Charleston, Illinois 61920
Combustion of White Phosphorus
Dr. Keiter completed his undergraduate work at Shepherd College in 1961 with a Bachelor of Science in chemistry. His undergraduate experience was enhanced by a summer internship at Ruberoid Corporation. He earned his master's degree in inorganic chemistry from West Virginia University in 1964 and his Ph.D. (with Samuel Grim) at the University of Maryland in 1967. This was followed by two years of post-doctoral research at Iowa State University (with John Verkade) that included one year of teaching general chemistry..
In 1969, Dr. Keiter joined the faculty at Eastern Illinois University, was named Professor of Chemistry in 1979, and Distinguished Professor in 1988, and Distinguished Professor Emeritus in 2007. He has served as Visiting Professor of Chemistry at the University of Wisconsin during the summers of 1972 and 1977 (with Bassam Shakhashiri), the University of Exeter (England) in 1975 (with Edward Abel), the University of Illinois in 1980 (with John Shapley), at Colorado State University in 1990 (with Jack Norton) and the University of Washington (2003). He taught inorganic chemistry while at the University of Illinois.
In 1998, Dr. Keiter received the Lawrence A. Ringenberg Award at Eastern Illinois University, the highest Award presented by the College of Sciences. In 1992 and again in 1998 he was the recipient of a Camille and Henry Dreyfus Foundation Scholar/Fellow Award. For nine years, he served as a Councilor of the Council on Undergraduate Research, where he was editor of the Inorganic Series and was an associate editor of the 1990 Research in Chemistry at Undergraduate Institutions. From 1992-1997, he served on the Petroleum Research Fund Advisory Board where he chaired the inorganic committee for non-Ph.D. schools and was a member of the Advisory Board policy committee.
Courses taught include general chemistry lecture and lab, honors general chemistry lecture and lab, sophomore descriptive inorganic chemistry, inorganic chemistry lecture and lab, organometallics, and group theory.
Born in the Shenandoah Valley near Winchester, Va., Dr. Keiter has spent his professional life in the Midwest. After passing through a decade of playing chess and another of doing triathlons, he and his wife (Ellen) joined Jim Huheey in revising his classic inorganic text, Inorganic Chemistry, Principles and Applications.
The Keiters’ son Eric is a Senior Member of the technical staff at Sandia National Laboratories in computational science and resides in Albuquerque, New Mexico; daughter Lise is a Professor of Piano Performance and Chair of the Music Department at Mary Baldwin College in Staunton, Virginia.
Research Interests
It had long been assumed that exchange of coordinated and uncoordinated phosphines in dangling ligand complexes, M(CO)5(L-L) (M = Cr, Mo, W) was insignificantly slow. It was reasoned that stability with respect to chelation also implied stability with respect to phosphine exchange. We have found that phosphorus exchange in (OC)5W[k1-PPh2CH2CH(PPh2)2] is sufficiently fast, even at room temperature, to prevent isolation of 1W in pure form.1
Intrigued by this highly unusual behavior, we initiated a kinetic and thermodynamic study. Our results show that isomer 2W is more stable than isomer 1W (ΔG298 = -3.86 kJ/mol), even though the more sterically demanding end of the phosphine ligand is coordinated in 2W. The entropy (ΔS‡ = -28.2 J K-1 mol-1) and enthalpy of activation (ΔH‡ = 92.6 kJ/mol) for the forward reaction strongly suggest a transition state that has an associative component. The rate constant for the forward reaction at 55oC is 3.7 x 10-4 s-1. For purposes of comparison we also studied phosphorus exchange in (OC)5W[k1-PPh2CH2CH2P(p-tol)2] 3W and found that the rate constant for isomerization is 3.3 x 10-8 s-1 (four orders of magnitude slower than for 1W). To account for the rate differences we have proposed a mechanism in which the initial step involves nucleophilic attack of a pendant phosphine on a carbonyl ligand leading to dissociation of the coordinated phosphine. The rate-determining step for 3W is a slow 1,2-shift leading to its linkage isomer. For 1W, a 1,2 shift is also possible but a much faster pathway is available. This entails coordination of the second dangling arm to give a 5-membered ring, which opens to give 2W.
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Complex 2W is less soluble than 1W and can be isolated by selective precipitation .The crystal structure shows a close approach of the short phosphine arm to a carbonyl group. The solution and solid state structures appear to be similar. |
Presently, we are continuing our thermodynamic and kinetic studies of phosphine exchange in dangling ligand complexes. These isomerization reactions are of fundamental importance because they suggest that complex reactivity may be profoundly influenced by the nature of pendant groups attached to a coordinated ligand.
Although it is widely recognized that the steric repulsion between pendant groups and other ligands of a complex may significantly influence reaction rates, the importance of attractive interactions between these groups and other ligands has received little attention. It would appear that for organometallic reactions in general, it may be possible to control substitution rates by employing ligands with pendant groups that have an affinity for other ligands attached to the central metal of the complex.
1Inorg. Chim. Acta 2010, 364, 176.
Publications (*Undergraduate coauthors)
Books
Huheey, J.E.; Keiter, E.A.; Keiter, R.L Anorganische Chemie – Prinzipien von Struktur und Reaktiviät, 4th ed. Walter de Gruyter, 2012, 1384 pp – revised by R. Steudel. Huheey, J.E.; Keiter, E.A.; Keiter, R.L Anorganische Chemie – Prinzipien von Struktur und Reaktiviät, 3rd ed. Walter de Gruyter, 2003, 1261 pp - Translated into German by R. Steudel. Huheey, J.E.; Keiter, E.A.; Keiter, R. Inorganic Chemistry, Principles of Structure and Reactivity , 4th Ed. Dorling Kindersley (India) - Pearson Education, South Asia, 2006, 806 pp – Modified by O.K. Medhi. (b) Huheey, J.E.; Keiter, E.A., Keiter, R.L. Inorganic Chemistry, Principles of Structure and Reactivity, International ed. Pearson Education, Taiwan Ltd, 2005, 964 pp. (c) Huheey, J.E.; Keiter, E.A.; Keiter, R.L Anorganische Chemie – Prinzipien von Struktur und Reaktiviät, 2nd ed. Walter de Gruyter, 2003, 1261 pp - Translated into German by R. Steudel. (d) Huheey, J.E.; Keiter, E.A.; Keiter, R.L Chimica Inorgaanica, Principl, Strutture, Reattivita, Piccin Nuova Librarie, Padova 1999, 1003 pp – translated into Italian by C. Botteghi. (e) Huheey, J.E.; Keiter, E.A., Keiter, R.L. Inorganic Chemistry, Freedom Academic, 1996, 1071 pp - Translated into Korean by G. Lee, D.-M. Kim, M.-Y. Park, Y.-K Shin, C.-N. Choi and H. Heo, F. (f) Keiter, E.A., Keiter, R.L. Quimica Inorganica, Principios de estructura y reactividad 4th ed. Oxford University Press, Mexico 1997, 1061 pp. (g) Huheey, J.E.; Keiter, E.A., Keiter, R.L. Chimie Inorganique, DeBoeck 1996, 964 pp - Translated into French by A. Pousse and J. Fischer, DeBoeck. (h) Huheey, J.E.; Keiter, E.A.; Keiter, R.L. Solutions to Problems, Inorganc Chemistry, Principles of Structure and Reactivity, HarperCollins, 1996,145 pp. (i) Huheey, J.E.; Keiter, E.A.; Keiter, R.L Anorganische Chemie – Prinzipien von Struktur und Reaktiviät, Walter de Gruyter, 1995, 1261 pp - Translated into German by R. Steudel. (j) Huheey, J.E.; Keiter, E.A., Keiter, R.L. Inorganic Chemistry, Principles of Structure and Reactivity, 4th ed. HarperCollins, New York, 1993, 964 pp
Keiter, E.A.; Keiter, R.L. A Study Guide for Chemistry, Matter, and the Universe W.A. Benjamin, Inc., Menlo Park, California 1976, 513 pp.
Hutton, W., Keiter, E.A.; Keiter, R.L., Teaching Assistance for Chemical Principles, W. A.Benjamin, Inc., Menlo Park, California 1974, 356 pp.
Keiter, R.L. Teaching Guide for Models in Chemical Science, W.A. Benjamin, Inc., Menlo Park, California 1971, 491 pp. German Translation (by Hans-Dieter Schenke), Walter de Gruyter and Co.,Berlin 1977.
ARTICLES ( *Undergraduate Coauthors)
Keiter, R.L.; Chen, D.; Holloway, G.A.; Keiter, E.A.; Zang, Y; * Huml, M.T.; Filley, J.S.; Brandt, D.E. “Intramolecular Exchange of Coordinated and Dangling Phosphine Groups in Pentacarbonyl[(diphenylphosphino)(di-p-tolylphosphino)methane]-tungsten(O) Organometallics 2012, 31, 4619.
Keiter, R.L.; Ye, P.; Keiter, E.A.; Benson, J.W.; Lin, W.; Brandt, D.E.; Southern, J.F.; Rheingold, A.L; Guzei, I.; *Wheeler, J.L; Cary L.W. “Intramolecular Exchange of Coordinated and Dangling Phosphines in Pentacarbonyl group 6 Complexes of 1,1,2 tris(diphenylphosphino) ethane,” Inorg. Chim. Acta 2010, 364, 176.
Keiter, R.L.; Reger, D.L. “Dedication to Professor Arnold L. Rheingold,” Inorg. Chim. Acta, 2010 364, 1.
Keiter, R.L.; *Puzey, W. L.; Blitz, E. A “Density Visualization,” J. Chem. Educ. 2006, 83, 1629.
Keiter, R.L.; *Martin, J.S.; Keiter, E.A.; Rheingold, A.L. “Crystal structure of trans-W2 (CO)6 (PPh2H)2 (μ2-PPh2)2,” J. Chem. Cryst. 2003, 33, 491.
Keiter, R.L.; Gamage, C. "The Combustion of White Phosphorus," J. Chem. Educ. 2001, 78, 908.
Keiter, R.L.; Benson, J. W.; Jia Z., Keiter, E.A.; Brandt, D.E. "Isomerization and Chelation Studies of (OC)5W[η1-PPh2CH2CH2P(p-tolyl)2] and (OC)5W[η1-P(p-tolyl)2CH2CH2 PPh2] (M = Cr, Mo, W),” Organometallics, 2000, 19, 4518.
Keiter, R.L.; Benson, J.W.; Keiter, E.A.; Lin, W.; Jia, Z.; *Olson, D.M.; Brandt, D.E.; *Wheeler, J.L., “Induced Acceleration of Phosphine Exchange in Metal Carbonyls by Pendant Groups of Coordinated Polyphosphines. Two Dangling Phosphine Arms Are Much Better Than One,” Organometallics, 1998, 17, 4291.
Benson, J.W.; Keiter, R.L.; Keiter, E.A.; Rheingold, A.L.; Yap, G.P.A.; Mainz, V.V. “Studies of a Reluctant Ligand. An X-ray Crystallographic and NMR Spectroscopic Analysis of (OC)5W(η1-PPh2CH2PPh2) and its (OC)5W(μ-PPh2CH2PPh2)W(CO)5 Derivative,” Organometallics, 1998, 17, 4275.
Keiter, R.L.; Benson, J.W.; Keiter, E.A.; *Harris, T.A.; *Hayner, M.W.; *Mosimann, L.L.; *Karch, E.E.; *Boecker, C.A.; *Olson, D.M.; *VanderVeen, J.; Brandt, D.E.; Rheingold, A.L.; Yap, G.P.A. “Phosphorus-Phosphorus Coupling Constants in Mixed-Phosphine Tricarbonyl Iron Complexes, Fe(CO)3LL’. Crystal Structure of trans- Fe(CO)3(PEt3)(PPh3),” Organometallics 1997, 16, 2246.
Keiter, R.L.; Keiter, E.A.; *Boecker, C. *Miller, D.; Hecker, K. "Tricarbonylbis(phosphine)-iron(O) Complexes" Inorg. Synth. 1997, 31, 210.
Benson, J.W.; Keiter, E.A.; Keiter, R.L. "On the Synthesis and 31P{1H} NMR Spectrum of (OC)5W(μ‑PPh2CH2PPh2)W(CO)5" J. Organomet.. Chem. 1995, 495, 77.
Keiter, R.L., Review of “Phosphorus-31 NMR Spectral Properties in Compound Characterization an Structural Analysis” in J. Am. Chem. Soc. 1995, 117, 7297.
Keiter, R.L.; Keiter, E.A.; *Olson, D.M.; *Bush, J.R.; Lin, W.; Benson, J.W. "Isomerization of (OC)5W[η1-PPh2CH2CH(PPh2)2]" Organometallics,1994, 13, 3752.
Anson, C.E.; Sheppard, N.; Powell, D.; Norton, J.R.; Keiter, R.L.; Fischer, W.; Johnson, B.F.G.; Lewis, J.; Bhattacharyya, K.; Knox, S.A.R.; Turner, M.L.; "An Assignment of the Infrared and Raman Spectra of the Os2(μ2‑CHCH3) Group of [(μ2‑CHCH3)Os2(CO)8], and Its d1 and d4 Isotopomers, as a Model for the Spectrum of an Ethylidene on a Metal Surface Pt(111)" J. Am. Chem. Soc. 1994, 116, 3058.
Keiter, R.L.; Keiter, E.A.; *Rust, M.S.; *Miller, D.R.; Sherman, E. O.; *Cooper, D.W. "Oxidation of Phosphido‑Bridged Complexes of Molybdenum and Tungsten. Isolation of [trans‑(HPh2P)(OC)3M(μ‑PPh2)2M(CO)3(PPh2H)][PF6] (M = Mo, W)" Organometallics 1992, 11, 487.
Keiter, R.L.; Keiter, E.A.; *Boecker, C.A.; *Miller, D.R. "The Synthesis Bis(phosphine)-tricarbonyliron(O) Complexes," Syn. React. Inorg. Metal‑Org. Chem 1991, 21(3), 473.
Keiter, R.L.; Keiter, E.A.; *Mittelberg, K.N.; *Martin, J.S.; *Meyers, V.M.; Wang, J.‑G. "Reactions of M(CO)6 (M = Mo, W) with PPh2H and NaBH4," Organometallics, 1989, 8, 1399.
Keiter, R.L.; Keiter, E.A.; Hecker, K.H.; *Boecker, C.A., "A Facile, High Yield Synthesis of trans‑Fe(CO)3(PR3)2 from Fe(CO)5, [Fe(CO)4CHO]‑, [HFe(CO)4]‑, or [HFe(CO)3PR3]‑," Organometallics 1988, 7, 2466.
Keiter, R.L., "Master's Programs at Non‑Ph.D Schools," Council on Undergraduate Research Newsletter 1988, 8, 56.
Keiter, R.L.; *Madigan, M.J., "Tetracarbonyl Group 6 Complexes Containing Secondary and Tertiary Phosphines," J. Organomet. Chem. 1987, 331, 341.
Keiter, R.L.; Strickland, D.S.; Wilson, S.R.; Shapley, J.R., "Cluster Complexes of H2Os3(CO)9(μ‑O3SO)," J. Am. Chem. Soc. 1986, 108, 3846.
Colquhoun, I.J.; McFarlane, W.; Keiter, R.L., "NMR Studies of Chelate Ring Effects in Tungsten(O) Carbonyl Complexes of Poly(tertiaryphosphines)," J. Chem. Soc., Dalton Trans. 1984, 455.
Keiter, R.L.; *Van der Velde, D.G., "Direct Observation of 183W NMR of W(CO)6 and Phosphine Derivatives," J. Organomet. Chem. 1983, 258, C34.
Keiter, R.L.; Rheingold, A.L.; Hamerski, J.J.; *Castle, C.K., "Unidentate Diphosphine Complexes, Crystal Structure and Molecular Geometry of Fe(CO)4(η1‑PPh2CH2CH2PPh2)," Organometallics 1983, 2, 1635.
Keiter, R.L., "Spectroscopically Silent Fundamental Vibrations," J. Chem. Educ. 1983, 60, 625.
Keiter, R.L.; *Borger, R.D.; *Madigan, M.J.; *Kaiser, S.L.; *Rowley, D., "The First Pan‑Group VI Transition Metal Complex: Synthesis (OC)5WPPh[CH2CH2PPh2][CH2CH2PPh2Cr(CO)5]," Inorg. Chim. Acta 1983, 76, L5.
Keiter, R.L.; *Madigan, M.J., "Synthesis and 31P NMR Characterization of [W2(CO)10PPh2]‑, W2(CO)9(PPh2H)(PPh2)]‑, [W2(CO)8(PPh2)2]2‑,and W2(CO)8(PPh2)2," Organometallics 1982, 1, 409.
Keiter, R.L.; *Brodack, J.W.; *Borger, R.D.; Cary, L.W., "Controlling the Number of Metal Sites to Which Ph2PCH2CH2PPhCH2CH2PPh2 Coordinates in Tungsten Carbonyls," Inorg. Chem. 1982, 21, 1256.
Ellis, J.W.; Keiter, E.A.; Keiter, R.L.; Li, T.P.; *Uptmor, R.A., "Reliable Synthesis of 1,1‑Dimethylpyrazolium 5‑oxides," J.Heterocycl. Chem. 1982, 19, 1215.
Keiter, R.L.; *Kaiser, S.L.; *Hansen, J.W.; *Brodack, J.W.; Cary, L.W., "Mixed Metal Carbonyl Complexes of Cr, Mo and W Containing Bridging PPh2CH2CH2PPh2," Inorg. Chem. 1981, 20, 283.
Churchill, M.R.; Rheingold, A.L.; Keiter, R.L., "Crystal Structure and Molecular Geometry of (OC)4WPPh2CH(CH2CH2PPh2)CH2PPh2·CH3CO2C2H5. Free Radical Addition of PPh2H to a Coordinated Phosphinoalkene," Inorg. Chem. 1981, 20, 2730.
Keiter, R.L.; Sun, Y.Y.; *Brodack, J.W.; Cary, L.W. "Controlling the Number of Metal Sites to Which a Di(tertiray phosphine) Coordinates in Group 6 Metal Carbonyls," J. Am. Chem. Soc. 1979, 101, 2638.
Keiter, R.L.; *Ahnger, T.; *Maurice, A.; *Baldwin, T. "The Preparation of Anhydrous Chromium(III) Chloride and the Pyrolysis of Carbon Tetrachloride," J. Chem. Educ. 1978, 55. 52.
Keiter, R.L.; *Borger, R.D.; Hamerski, S.J.; *Garbis, S.J.; *Leotsakos, G.S. "Ditertiary Phosphines as Monodentate Ligands in Transition Metal Carbonyl Complexes," J. Am. Chem. Soc. 1977, 99, 5224.
Keiter, R.L.; *Benedik, Jr., J.E.; Cary, L.W. "A Bimetallic Carbonyl Complex of Nickel and Tungsten," Inorg. Nucl. Chem. Letters 1977, 13, 455.
Keiter, R.L.; Abel, E.W. "Reactions of Tertiary Phosphines with (CH3)3SnCH2I," J. Organomet. Chem. 1976, 107, 73.
Keiter, R.L.; *Fasig, K.E.; Cary, L.W., "Tungsten Carbonyl Complexes as Ligands," Inorg. Chem. 1975, 14, 201.
Keiter, R.L.; Marcovich, D. "Zwitterionic Carbonyl Halide Complexes of Tungsten," Inorg. Nucl. Chem. Letters 1974, 10, 1099.
Taylor, R.C.; Keiter, R.L.; Cary, L.W., "A Phosphorus‑31 Nuclear Magnetic Resonance Study of Tungsten Carbonyl Complexes Containing Unsaturated Organophosphorus Cationic Ligands," Inorg. Chem. 1974, 13, 1928.
Grim, S.O.; Lui, P.J.; Keiter, R.L., "Phosphorus‑31 Nuclear Magnetic Resonance Study of Tertiary Phosphine‑Mercury(II) Halide Complexes," Inorg. Chem. 1974, 13, 342.
Keiter, R.L.; Cary, L.W., "A Phosphorus‑3l Nuclear Magnetic Resonance Study of Tungsten Carbonyl Complexes Containing Positively Charged Phosphorus Ligands. Observation of 3JWP," J. Am. Chem. Soc. 1972, 94, 9232.
Keiter, R.L.; Shah, D.P. "Tungsten Carbonyl Complexes Containing Positively Charged Phosphorus Ligands," Inorg. Chem. 1972, 11, 191.
Fischer, E.O.; Knauss, L.; Keiter, R.L.; Verkade, J.G. "Tungsten‑183‑Phosphorus‑31 Spin‑Spin coupling Interactions in Phosphorus Trihalide Pentacarbonyltungsten Complexes," J. Organomet. Chem. 1972, 37, C7.
Grim, S.O.; Molenda, R.P.; Keiter, R.L., "A Novel Synthesis of Unsymmetrical Ditertiary Phosphines," Chem. and Ind. 1970, 1378.
Grim, S.O.; Keiter, R.L., "A Phosphorus‑3l Magnetic Resonance Study of Tertiary Phosphine Palladium(II) Compounds," Inorg. Chim. Acta. 1970, 9, 56.
Keiter, R.L.; Verkade, J.G., "Metal‑Phosphorus Stretching Frequencies of Some Tetrakis(bicylic phosphite) Complexes of Nickel(O), Palladium(O), Platinum(O), Copper(I) and Silver(I)," Inorg. Chem. 1970, 9, 404.
Keiter, R.L.; Verkade, J.G. "Tungsten‑l83‑Phosphorus‑31 Spin‑Spin Coupling Interactions in Pentacarbonyltungsten Complexes," Inorg.Chem. 1969, 8, 2115.
Ogilvie, F.B.; Keiter, R.L.; *Wulfsberg, G.; Verkade, J.G. "Phosphorus‑31 Coupling in Metal Complexes Containing Two Different Phosphorus Ligands," Inorg. Chem. 1969, 8, 2346.
Keiter, R.L.; Grim, S.O. "Mercury‑l99‑Phosphorus‑3l Nuclear Spin‑Spin Coupling in Tertiary Phosphine Complexes of Mercury(II) Bromide," Chem Comm. 1968, 521.
Grim, S. O.; Keiter, R.L.; McFarlane, W. "A Phosphorus‑31 Nuclear Magnetic Resonance Study of Tertiary Phosphine Complexes of Platinum(II)," Inorg. Chem., 1967, 6, 1133.
Combustion of White Phosphorus
Keiter, R.L.; Gamage, C. "The Combustion of White Phosphorus," J. Chem. Educ., 2001, 78, 908-910.
| Initial Reaction | Reaction At Maximum Brilliance |
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