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Title: Eight coordinate 1,2-bis(dimethylarsino) and 1,2-bis(dimethylphosphino)-benzene complexes of uranium tetrachloride, UCl 4 [(1,2-Me 2 E) 2 C 6 H 4 ] 2 where E is As or P

Authors:
; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1359782
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 116; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-04 09:14:07; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Rozenel, Sergio S., Edwards, Peter G., Petrie, Mark A., and Andersen, Richard A. Eight coordinate 1,2-bis(dimethylarsino) and 1,2-bis(dimethylphosphino)-benzene complexes of uranium tetrachloride, UCl 4 [(1,2-Me 2 E) 2 C 6 H 4 ] 2 where E is As or P. United Kingdom: N. p., 2016. Web. doi:10.1016/j.poly.2016.04.024.
Rozenel, Sergio S., Edwards, Peter G., Petrie, Mark A., & Andersen, Richard A. Eight coordinate 1,2-bis(dimethylarsino) and 1,2-bis(dimethylphosphino)-benzene complexes of uranium tetrachloride, UCl 4 [(1,2-Me 2 E) 2 C 6 H 4 ] 2 where E is As or P. United Kingdom. doi:10.1016/j.poly.2016.04.024.
Rozenel, Sergio S., Edwards, Peter G., Petrie, Mark A., and Andersen, Richard A. 2016. "Eight coordinate 1,2-bis(dimethylarsino) and 1,2-bis(dimethylphosphino)-benzene complexes of uranium tetrachloride, UCl 4 [(1,2-Me 2 E) 2 C 6 H 4 ] 2 where E is As or P". United Kingdom. doi:10.1016/j.poly.2016.04.024.
@article{osti_1359782,
title = {Eight coordinate 1,2-bis(dimethylarsino) and 1,2-bis(dimethylphosphino)-benzene complexes of uranium tetrachloride, UCl 4 [(1,2-Me 2 E) 2 C 6 H 4 ] 2 where E is As or P},
author = {Rozenel, Sergio S. and Edwards, Peter G. and Petrie, Mark A. and Andersen, Richard A.},
abstractNote = {},
doi = {10.1016/j.poly.2016.04.024},
journal = {Polyhedron},
number = C,
volume = 116,
place = {United Kingdom},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.poly.2016.04.024

Citation Metrics:
Cited by: 1work
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  • The titled compounds were synthesized and their molecular structures determined by single-crystal x-ray diffraction. The crystal parameters are reported. Both complexes are unimolecular in the crystalline state. The U(IV) atom is coordinated to 4 BH/sub 3/CH/sub 3/ groups through the tridentate hydrogen bridges and to two P atoms of tertiary P ligands. The U(III) complex is coordinated to three BH/sub 3/CH/sub 3/ groups through tridentate hydrogen bridges and to four P atoms from the tertiary P ligands. The U-B distances for the U(IV) and U(III) complexes average 2.57 +/- 0.01 and 2.63 +/- 0.02 A, respectively; the U-P distances formore » the U(IV) and U(III) complexes average 3.02 +/- 0.01 and 3.13 +/- 0.06 A, respectively.« less
  • The use of a reduction-substitution route to prepare the thiolato-technetium(III) complexes trans-(Te(SR){sub 2}(DMPE){sub 2}){sup +} from the technetium(V) starting material trans-(Tc(OH)(O)(DMPE){sub 2}){sup 2+} and alkane- or benzenemethanethiols has been investigated (DMPE represents 1,2-bis(dimethylphosphino)ethane). The four newly prepared trans-(Tc(SR){sub 2}(DMPE){sub 2}){sup +} complexes (R = C{sub 2}H{sub 5}, n-C{sub 3}H{sub 7}, CH{sub 2}C{sub 6}H{sub 5}, CH{sub 2}C{sub 6}H{sub 4}-p-OCH{sub 3}) are characterized by fast atom bombardment mass spectrometry, visible-uv spectrophotometry, spectroelectrochemistry, and elemental analyses of three examples. They are assigned a trans geometry by comparison with the known structure of trans-(Tc(SCH{sub 3}){sub 2}(DMPE){sub 2}){sup +}. All five thiolato complexes exhibit amore » reversible Te(III/II) couple at about -0.5 V, a reversible Tc(II/I) couple at about -1.8 V, and an irreversible redox process at about +0.9 V that is tentatively assigned as resulting from a metal-based Tc(IV/III) couple (all potentials obtained in 0.5 M TEAP/DMF vs Ag/AgCl (3 M NaCl)). The potentials of all three couples are dependent on the nature of the thiolato R group; e.g., the Tc(III/II) couple varies from -0.513 V for R = benzyl to -0.622 V for R = n-propyl. For both the Tc(III) and Tc(II) complexes the visible spectra are dominated by sulfur-to-technetium charge-transfer transitions, the energies of which depend on the technetium oxidation state but do not depend on the nature of the thiolato R group. Observations on the relative instability of trans-(Tc(SCH{sub 3}){sub 2}(DMPE){sub 2}){sup +} in 0.5 M TEAP/DMF are interpreted in terms of the possible existence of the cis isomer of this complex. 25 refs., 6 figs., 4 tabs.« less
  • The Tc(III) methanethiolato complexes trans-(Tc(SCH/sub 3/)/sub 2/D/sub 2/)/sup +/, where D is either 1,2-bis(dimethylphosphino)ethane (DMPE) or 1,2-bis(diethylphosphino)ethane (DEPE), have been synthesized and characterized. Preparation of these complexes from (Tc/sup V/(O)(OH)D/sub 2/)/sup 2+/ utilizes excess NaSCH/sub 3/ as reductant and ligand. The x-ray crystal structures of both title complexes are examined, and the crystal parameters are reported. In both structures the Tc atom occupies an inversion center. The visible spectra of these trans-(Tc(SCH/sub 3/)/sub 2/D/sub 2/)/sup +/ complexes in acetonitrile show sulfur-technetium charge-transfer bands at 16,810 and 28,490 cm/sup /minus/1/ for D = DMPE and at 16,610 and 28,830 cm/sup /minus/1/more » for D = DEPE. Cyclic voltammetric measurements in N,N-dimethylformamide show two reversible reduction couples corresponding to Tc(III/II) and Tc(II/I) at -0.550 and -1.72 V vs Ag/AgCl for D = DMPE and -0.554 and -1.81 V vs Ag/AgCl for D = DEPE. The absorption spectra and cyclic voltammograms are compared with those of other trans-(TcD/sub 2/X/sub 2/)/sup +/ complexes with X = Cl, Br, -NCS and are discussed in terms of the relative strengths of the /simga/ and /pi/ interactions between Tc and the ligating S and P atoms. 45 refs., 5 figs., 8 tabs.« less
  • Pulse radiolytic techniques have been employed to study the rate of reactions of the strong reductant e{sub aq}{sup {minus}} and the strong oxidant Cl{sub 2}{sup {minus}} with lipophilic, cationic Tc and Re complexes in aqueous and aqueous surfactant media. In aqueous media the reaction of the M(III) complexes trans-(Re{sup III}Cl{sub 2}(DMPE){sub 2}){sup +}, trans-(Re{sup III}Br{sub 2}(DMPE){sub 2}){sup +}, and trans-(Tc{sup III}Cl{sub 2}(DMPE){sub 2}){sup +} have been studied with both reagents, while the reaction of the M(I) complexes (Re{sup I}(DMPE){sub 3}){sup +} and (Tc{sup I}(DMPE){sub 3}){sup +} have been studied with Cl{sub 2}{sup {minus}}. Oxidation of the M(I) complexes cleanly yieldsmore » the corresponding (M{sup II}(DMPE){sub 3}){sup +} species by an outer-sphere mechanism, whereas oxidation of the M(III) complexes appear to proceed by more complicated pathways, which could involve outer-sphere electron transfer as well as oxidative addition. All reactions proceed at or near the diffusion-controlled limit. The positively charged surfactant CTAB (Hexadecyltrimethylammonium bromide) and the uncharged surfactant Triton X-100 ({alpha}-(p-(1,1,3,3-tetra-methylbutyl)phenyl)-{omega}-hydroxypolyoxyethylene(9.5)) have little or no effect on the rates of any of the reactions studied. However, micelles formed from the negatively charged surfactant SDS (sodium dodecyl sulfate) exert a dramatic effect on reaction rates by effectively sequestering the cationic complexes and rendering them relatively unavailable for reaction with the anionic reagents e{sub aq}{sup {minus}} and Cl{sub 2}{sup {minus}}. While the anionic reagents can penetrate the SDS micelles, the cationic complexes do not appear to be released from the micelle during the lifetime of the anionic radicals (ca. 10{sup 2} {mu}s). These results have implications for the use of surfactants in electrochemical studies, as well as for the pharmacokinetics of cationic complexes of interest to nuclear medicine.« less