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Macrocyclic rhodium(III) hydrides and a monomeric rhodium(II) complex

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic960300a· OSTI ID:473998
;  [1]
  1. Iowa State Univ., Ames, IA (United States)
Several mononuclear N{sub 4}-macrocyclic Rh(III) hydrides were prepared and characterized in the solid state and in solution. H NMR, IR, and UV data are reported. The complex [trans-(Cl)([14]aneN{sub 4})RhH]{sub 2}(ZnCl{sub 4}){center_dot}dmso(1{center_dot}dmso) crystallizes in the triclinic system, space group P1, in a unit cell of dimension a = 10.680 {Angstrom}, b = 13.460 {Angstrom}, c= 14.277 {Angstrom}, {alpha} = 86.49{degrees}, {beta} = 83.18{degrees}, {gamma} = 66.64{degrees}. The data refined to a final value of R=0.070 and R{sub w} = 0.13 based on 2687 observed reflections. UV photolysis of chloride-free (H{sub 2}O)L{sup 1}RhH{sup 2+} results in homolytic Rh-H bond cleavage. The rhodium(II) product, L{sup 1}Rh(H{sub 2}O){sup 2+}, was characterized by ESR and UV spectroscopies. This species survives in acidic aqueous solution for over half an hour at room temperature. The photolysis of (H{sub 2}O)L{sup 1}RhH{sup 2+} in the presence of O{sub 2} produces the superoxorhodium(III) ion, trans-L {sup 1}RhOO{sup 2+}.
OSTI ID:
473998
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 20 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English