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Reactivity patterns of transition metal hydrides and alkyls

Description: The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.
Date: May 1, 1979
Creator: Jones, W. D., II
Partner: UNT Libraries Government Documents Department

Transition metal activation and functionalization of carbon-hydrogen bonds

Description: We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.
Date: June 1, 1992
Creator: Jones, W.D.
Partner: UNT Libraries Government Documents Department

Transition metal activation and functionalization of carbon-hydrogen bonds. Progress report, December 1, 1989--November 30, 1992

Description: We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.
Date: June 1, 1992
Creator: Jones, W. D.
Partner: UNT Libraries Government Documents Department

Testing of hollow clay tile masonry prisms

Description: This paper presents test results of 610-mm wide (24-in.) by 1219-mm high (48-in.) by 203-or 330-mm (8- or 13-in.) thick prisms constructed of hollow clay tiles. Three prisms were extracted fro existing hollow clay title walls and 69 were constructed in laboratories at The University of Tennessee and the National Institute of Standards and Technology (NIST) in Gaithersburg, Maryland. Modulus of Elasticity, E, and compressive strength f{prime}{sub m} were calculated from the results.
Date: October 15, 1993
Creator: Jones, W. D. & Butala, M. B.
Partner: UNT Libraries Government Documents Department

Development of site-specific synthetic accelerations for safety assessment of DOE facilities at Oak Ridge, Tennessee

Description: Seismic analysis of US Department of Energy (DOE) facilities at Oak Ridge, TN, requires seismic accelerograms that have response spectra that are compatible with the site-specific design response spectra. The development of these accelerograms is accomplished by the application of the Fourier transform to compute the response spectrum of a beginning accelerogram and map it into the frequency domain. The Fourier spectrum is modified according to the difference between the computed spectra and the target spectra. The response spectrum is recomputed and compared again to the target. The modification is repeated until acceptable agreement is achieved. The modified Fourier spectrum is transformed to the time domain and filtered yielding the desired seismic time history. 7 refs., 5 figs.
Date: January 1, 1991
Creator: Aramayo, G.A.; Carley, T.G. & Jones, W.D.
Partner: UNT Libraries Government Documents Department

Out-of-plane behavior of hollow clay tile walls infilled between steel frames

Description: Several buildings at Y-12 Plant rely on unreinforced hollow clay tile walls (HCTW) infilled between unbraced, non-moment resisting steel frames to resist natural phenomena forces, seismic and wind. One critical building relies on moment resisting steel frames in one direction while relying on unreinforced HCTWs infilled between the columns in the orthogonal direction to resist these forces. The HCTWs must act as shear walls while maintaining out-of-plane lateral stability. In assessing the safety of these buildings to seismic forces, several models to study the in- and out-of-plane effects were made and analyzed. The study of the moment resisting steel framed building indicated that bending stresses in the walls were induced by building drift and not by inertial forces per se. The discovery of this phenomenon was some what of a surprise in that the analysis performed is not typically used in design of these structures. The study indicated that the walls began to crack at their interface with the foundation at a low ``g`` level and that horizontal cracking at different elevations continued until the walls exhibited little bending resistance. This paper presents results of the study for out-of-plane behavior of unreinforced HCTWs infilled between adjacent moment resisting steel frames and discusses the problems of assessing the in-plane behavior given the horizontal cracks induced by building drift in the out-of-plane direction.
Date: August 16, 1991
Creator: Butala, M.B.; Jones, W.D. & Beavers, J.E.
Partner: UNT Libraries Government Documents Department

Hollow clay tile wall program summary report

Description: Many of the Y-12 Plant buildings, constructed during the 1940s and 1950s, consist of steel ed concrete framing infilled with hollow clay tile (HCT). The infill was intended to provide for building enclosure and was not designed to have vertical or lateral load-carrying capacity. During the late 1970s and early 1980s, seismic and wind evaluations were performed on many of these buildings in conjunction with the preparation of a site-wide safety analysis report. This analytical work, based on the best available methodology, considered lateral load-carrying capacity of the HCT infill on the basis of building code allowable shear values. In parallel with the analysis effort, DOE initiated a program to develop natural phenomena capacity and performance criteria for existing buildings, but these criteria did not specify guidelines for determining the lateral force capacity of frames infilled with HCT. The evaluation of infills was, therefore, based on the provisions for the design of unreinforced masonry as outlined in standard masonry codes. When the results of the seismic and wind evaluations were compared with the new criteria, the projected building capacities fell short of the requirements. Apparently, if the buildings were to meet the new criteria, many millions of dollars would be required for building upgrades. Because the upgrade costs were significant, the assumptions and approaches used in the analyses were reevaluated. Four issues were identified: (1) Once the infilled walls cracked, what capacity (nonlinear response), if any, would the walls have to resist earthquake or wind loads applied in the plane of the infill (in-plane)? (2) Would the infilled walls remain within the steel or reinforced concrete framing when subjected to earthquake or high wind loads applied perpendicular to the infill (out-of-plane)? (3) What was the actual shear capacity of the HCT infill? (4) Was modeling the HCT infill as a ...
Date: July 30, 1995
Creator: Henderson, R.C.; Jones, W.D. & Beavers, J.E.
Partner: UNT Libraries Government Documents Department

The Effect of Prior Out-of-Plane Damage on the in-Plane Behavior of Unreinforced Masonry Infilled Frames

Description: In order to address the effect of prior out-of-plane damage on the in-plane behavior of unreinforced masonry infills, two full-scale (24 feet tall by 28 feet long) structural clay tile infills and one frame-only (no infilling) were constructed and tested. The infilled frame, consisting of two wide flange columns surrounded by masonry plasters and an eccentric wide flange purlin, was identical to many of the infills located at the Oak Ridge Y-12 Plant. The masonry infill was approximately 12.5 inches thick and was composed of individual four- and eight-inch hollow clay tile (HCT) units. One of the infill panels was tested out-of-plane by four quasi-static actuators -- two on each column. The test structure was deflected out-of-plane equally at all four actuator locations in order to simulate the computed deflection path of the top and bottom chords of a roof truss framing into the columns at these locations. Prior to the infill testing, a bare frame was loaded similarly in order to determine the behavior and stiffness contribution of the frame only. Following the out-of-plane test of the infilled panel, the structure was loaded in-plane to failure in order to ascertain residual strength. A second, identical infilled frame was then constructed and tested in-plane to failure. In this way, in-plane behavior with and without prior out-of-plane damage could be established and compared. For both out-of-plane and in-plane testing, reversed-cyclic quasi-static loading was used in order to obtain full tension/compression hystereses. Also, natural frequencies of the first infilled panel were determined before and after the out-of-plane testing. This paper describes the test series and discusses the conclusions pertinent to the effect of out-of-plane cracking on in-plane stiffness and behavior.
Date: August 25, 1993
Creator: Henderson, R. C.; Jones, W. D.; Burdette, E. G. & Porter, M. L.
Partner: UNT Libraries Government Documents Department