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Complexes Having the fac-{M(CO)3}+ Core (M = Tc, Re) Useful in Radiopharmaceuticals:  X-ray and NMR Structural Characterization and Density Functional Calculations of Species Containing Two sp3 N Donors and One sp3 O Donor

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Department of Radiology, Emory University, Atlanta, Georgia 30322, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, and Department of Chemical and Biosystem Sciences and Technologies, University of Siena, I-53100 Siena, Italy
Cite this: Inorg. Chem. 2004, 43, 24, 7774–7783
Publication Date (Web):October 23, 2004
https://doi.org/10.1021/ic049544i
Copyright © 2004 American Chemical Society

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    Radiopharmaceuticals containing the “fac-{M(CO)3}+” core (M = 99mTc, 186Re, or 188Re) have potential as diagnostic or therapeutic agents. Complexes with this core with sp3 amine donors have received little attention. We have studied adducts formed by ENDACH2 (HO2CCH2NHCH2CH2NHCH2CO2H) and ENACH (NH2CH2CH2NHCH2CO2H). Re(CO)3(ENDACH)-A (1A) and Re(CO)3(ENDACH)-B (1B) isomers were obtained by the reaction of ENDACH2 with Re(CO)5Cl. Re(CO)3(ENAC) (2) was obtained by the reaction of ENACH with aqueous [Re(CO)3(H2O)3]+. From single-crystal X-ray data, the three new neutral complexes, 1A, 1B, and 2, have a six-coordinate, pseudo-octahedral Re center with facially coordinated carbonyl ligands. ENDACH- and ENAC- bind facially to Re through both amine nitrogens and one carboxyl oxygen, forming two five-membered chelate rings. The Re(CO)3(ENDACH) isomers have an uncoordinated, dangling −CH2CO2H group, which is an ideal coupling site for attachment to biomolecules. The isomers differ by the configuration of the NH center bearing this dangling group. The H atom of the amine (N2) is endo (near the carbonyl ligands in the basal plane) in 1A and exo (away from carbonyl ligands) in isomer 1B. Isomers reach equilibrium (1A:1B, 70:30) after 3 days at high pH. Density functional structure optimizations were performed for isolated molecules of the type TcI/ReI(CO)3(N2O):  [Re(CO)3(NH3)2(H2O)]+, [Tc(CO)3(NH3)2(H2O)]+, [Re(CO)3(EN)(H2O)]+ (EN, ethylenediamine), [Tc(CO)3(EN)(H2O)]+, and various models for 1A, 1B, and 2. The computed structures are in good agreement with the X-ray structures. The theoretical and experimental Re−N bond distances usually agree within 0.045 Å. The total electronic energy values for the computed 1A and 1B models differ by 0.815 kcal mol-1, giving an isomer ratio of 80:20, in good agreement with the 1A/1B ratio (70:30) found.

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     Emory University.

     University of Siena.

    §

     Louisiana State University.

    *

     Author to whom correspondence should be addressed. Phone:  225-578-0933. Fax:  225-578-3463. E-mail:  [email protected].

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    Additional explanations of NMR shifts employing Newman projections. Tables of atomic coordinates for structures computed via DFT methods. X-ray crystallographic data for 1A, 1B, and 2 in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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