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Synthesis and Structure of Technetium Trichloride

Journal Article · · J. Am. Chem. Soc.
DOI:https://doi.org/10.1021/ja105730e· OSTI ID:1002913
Technetium trichloride has been synthesized by reaction of Tc{sub 2}(O{sub 2}CCH{sub 3}){sub 4}Cl{sub 2} with HCl(g) at 300 C. The mechanism of formation mimics the one described earlier in the literature for rhenium. Tc{sub 2}(O{sub 2}CCH{sub 3}){sub 2}Cl{sub 4} [P{sub T}; a = 6.0303(12) {angstrom}, b = 6.5098(13) {angstrom}, c = 8.3072(16) {angstrom}, {alpha} = 112.082(2){sup o}, {beta} = 96.667(3){sup o}, {gamma} = 108.792(3){sup o}; Tc-Tc = 2.150(1) {angstrom}] is formed as an intermediate in the reaction at 100 C. Technetium trichloride is formed above 250 C and is isostructural with its rhenium homologue. The structure consists of Tc{sub 3}Cl{sub 9} clusters [R{sub 3}m; a = b = 10.1035(19) {angstrom}, c = 20.120(8) {angstrom}], and the Tc-Tc separation is 2.444(1) {angstrom}. Calculations on TcX{sub 3} (X = Cl, Br) have confirmed the stability of TcCl{sub 3} and suggest the existence of a polymorph of TcBr{sub 3} with the ReBr{sub 3} structure.
Research Organization:
Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
Sponsoring Organization:
USDOE
OSTI ID:
1002913
Journal Information:
J. Am. Chem. Soc., Journal Name: J. Am. Chem. Soc. Journal Issue: (45) ; 11, 2010 Vol. 132; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
ENGLISH

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