Synthesis, characterization, and crystal structure of neutral rhenium(V) complexes with S-substituted N{sub 2}S{sub 2} ligands
- Medi-Physics, Inc., Emeryville, CA (United States)
- Hoffmann-La Roche, Nutley, NJ (United States)
Rhenium is technetium`s third row congener and exhibits many of the chemical properties that technetium displays. Theoretically, a Re-PhAT complex will be isostructural with the {sup 99m}Tc PhAT complexes that have been prepared for use as brain imaging agents. A series of neutral rhenium(V) oxo complexes was synthesized by the reaction of ReOBr{sub 4}{sup {minus}} with diamino-thiol-thioether ligands of the type (RSC(CH{sub 3}){sub 2})CH{sub 2}NH(o-C{sub 6}H{sub 4})NHCH{sub 2}C(CH{sub 3}){sub 2}SH. The complexes were characterized by IR, UV/visible, and {sup 1}H and {sup 13}C NMR spectroscopy and by fast-atom-bombardment mass spectroscopy. The single-crystal X-ray structure determination on two of the complexes, where R = CH{sub 2}CH{double_bond}CH{sub 2} and CH{sub 2}CH{sub 2}-CH{sub 3}, showed them to consist of a square pyramidal Re{sup V}ON{sub 2}S{sub 2} core. ReO[CH{sub 2}{double_bond}CHCH{sub 2}SC(CH{sub 3}){sub 2}CH{sub 2}N(o-C{sub 6}H{sub 4})NCH{sub 2}C(CH{sub 3}){sub 2}S], C{sub 17}H{sub 25}N{sub 2}OS{sub 2}Re, crystallizes in the monoclinic space group P2{sub 1}/a with {alpha} = 17.899(3) {angstrom}, b = 13.910(1) {angstrom}, c = 15.936(1) {angstrom}, {beta} = 104.70(1){degrees}, Z = 8, D{sub calc} = 1.813 g cm{sup {minus}3}, and {mu}(Cu K{alpha}) = 139.8 cm{sup {minus}1}. The propyl complex, C{sub 17}H{sub 27}N{sub 2}OS{sub 2}Re, crystallizes in the monoclinic space group P2{sub 1}/a with a = 18.076(1) {angstrom}, b = 13.920(1) {angstrom}, c = 15.994(1) {angstrom}, {beta} = 105.09(1){degrees}, Z = 8, D{sub calc} = 1.797 g cm{sup {minus}3}, and {mu}(Cu K{alpha}) = 138.0 cm{sup {minus}1}. The combination of the steric and electronic effects of the aromatic ring fused to the backbone of the N-C-C-N ligand and the S-substitution result in deprotonation of both amine nitrogens and coplanarity of the base of the square pyramidal complex.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 47960
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 24; Other Information: PBD: 23 Nov 1994
- Country of Publication:
- United States
- Language:
- English
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