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Author Bullock, R. M. ♦ Koetzle, T. F. ♦ Schultz, A. J.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ MANGANESE COMPLEXES ♦ CRYSTAL STRUCTURE ♦ CHEMICAL REACTIONS ♦ RHENIUM COMPLEXES ♦ HYDRIDES ♦ CARBONYLS ♦ MONOCLINIC LATTICES ♦ CHEMICAL PREPARATION ♦ MOLECULAR STRUCTURE ♦ NEUTRON DIFFRACTION ♦ EQUILIBRIUM
Abstract The crystal and molecular structure of (CO){sub 5}Re({mu}-H)Mn(CO){sub 4}Mn(CO){sub 5}, prepared from reaction of Mn{sub 2-} (CO){sub 9}({eta}{sup 1}-tolualdehyde) with HRe(CO){sub 5}, has been determined from neutron diffraction measurements at 15K: unit-cell constants, a = 9.145 (1) {angstrom}, b = 15.557 (3) {angstrom}, c = 14.040 (3) {angstrom}, {beta} = 106.60 (2){degrees}, monoclinic, space group P2{sub 1}/n, Z = 4, V = 1914.2 (6) {angstrom}{sup 3}. R(F{sup 2}) = 0.110 for 4859 reflections with F{sub 0}{sup 2}{ge}3{sigma}(F{sub 0}{sup 2}) and (sin {theta}/{lambda}){sub max} = 1.054 {angstrom}{sup -1}. The Re-H distance (1.827 (4) {angstrom}) is longer than the Mn-H distance (1.719 (5) {angstrom}). Spectroscopic and crystallographic data indicate that a small amount ({approximately}9%) of (CO){sub 5}Re({mu}-H)Mn(CO){sub 4}Re(CO){sub 5} has cocrystallized with the major component. Further evidence for the identity of (CO){sub 5}Re({mu}-H)Mn(CO){sub 4}Re(CO){sub 5} comes from an independent synthesis by a known route. A mechanism if proposed that accounts for the formation of (CO){sub 5}Re({mu}-H)Mn(CO){sub 5} from the reaction of (CO){sub 5}Re({mu}-H)Mn(CO){sub 4}Mn(CO){sub 5} with HRe(CO){sub 5}. The equilibrium constant for the metal-metal exchange equilibrium, (CO){sub 5}Re({mu}-H) Mn(CO){sub 4}Mn(CO){sub 5}+HRe(CO){sub 5} = (CO){sub 5}Re({mu}-H)Mn(CO){sub 5} + HMn(CO){sub 5}, has been determined; K{sub eq} = 1.00 {+-} 0.05 at 22 {degrees}C in C{sub 6}D{sub 6}. 36 refs., 3 figs., 3 tabs.
ISSN 00027863
Educational Use Research
Learning Resource Type Article
Publisher Date 1992-06-17
Publisher Department Brookhaven National Laboratory (BNL), Upton, NY
Publisher Place United States
Journal Journal of the American Chemical Society
Volume Number 114
Issue Number 13
Organization Brookhaven National Laboratory (BNL), Upton, NY


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