Synthesis and Characterization of Organohydrazino Complexes of Technetium, Rhenium, and Molybdenum with the {M(η1-HxNNR)(η2-HyNNR)} Core and Their Relationship to Radiolabeled Organohydrazine-Derivatized Chemotactic Peptides with Diagnostic Applications

David J. Rose, Kevin P. Maresca, Terrence Nicholson, Alan Davison, Alun G. Jones, John Babich, Alan Fischman, Wendy Graham, Jeffery R.D. DeBord, Jon Zubieta

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Abstract

The reduction of perrhenate, molybdate and pertechnetate with 2-hydrazinopyridine dihydrochloride in methanol has led to the preparation of a class of complexes containing the {M(η1-NNC5H4NHx)(η 2-HNNHyC5H4N)} core, represented by [TcCl3(NNC5H4NH)(HNNC5H 4N)] (2), [ReCl3(NNC5H4NH)(HNNC5H 4N)] (3), and [MoCl3(NNC5H4NH)(HNNHC5H 4N)] (6). The reaction of 3 with NEt3 results in the formation of [HNEt3][[ReCl3(NNC55H4N)(HNNC 5H4N)]·H2O (4) by deprotonation of the pyridine nitrogen site. Similarly, the reduction of perrhenate with 2-hydrazino-2-imidazoline hydrobromide has led to the preparation of the analogous [ReCl3(NNC3H4N2H)(HNNHC 3H4N2H)] (5). Reaction of 3 with pyridine-2-thiol and pyrimidine-2-thiol yields two structurally characterized derivatives with a modified {Re(η1-NNC5H4N)(η2-HNNC 5H4N)} core, [Re(C5H4NS)2(NNC5H 4N)(HNNC5H4N)] (8) and [Re(C4H3N2S)2(NNC5H 4N)(HNNC5H4N)] (9), respectively. Reaction of 6 with pyrimidine-2-thiol led to the isolation of the analogous [Mo(C4H3N2S)2(NNC5H 4N)(HNNHC5H4N)] (11) and the seven-coordinate monohydrazine core complex [Mo(C4H3N2S)3(NNC5H 4N)]·CH2Cl2 (12). In similar fashion, the reaction of 2 with pyridine-2-thiol yielded a complex structurally analogous to 8, [Tc(C5H4NS)2(NNC5H 4N)(HNNC5H4N)] (7). Crystal data for 3, C10H10Cl3N6Re: triclinic, P1̄, a = 7.527(2) Å, b = 7.599(2) Å, c = 13.118(3) Å, α = 106.55(3)°, β= 90.28(3)°, γ = 93.83(3)°, V = 717.4(4) Å3, Z = 2. For 4, C16H27Cl3N7ORe: orthorhombic, P212121, a = 7.503(2) Å, b = 10.3643(2) Å, c = 30.1590(5) Å, V = 2345.20(6) Å3, Z = 2. For 5, C6H12Cl3N8Re: monoclinic, P21/n, a = 9.093(2) Å, b = 11.105(2) Å, c = 14.295(3) Å, β = 94.71(3)°, V = 1438.6(7) Å3, Z = 4. For 6, C10H11Cl3N6Mo: monoclinic, P21/c, a = 15.366(3) Å, b = 7.804(2) Å, c = 12.378(3) Å, β = 95.92(3)°, V = 1476.4(5) Å3, Z = 4. For 7, C20H17N8S2Tc: monoclinic, P21, a = 8.827(2) Å, b = 9.278(2) Å, c = 13.304(3) Å, β= 98.92(3)°, V = 1076.5(5) Å3, Z = 2, 2564 reflections. For 8, C20H17N8S2Re: monoclinic, P21, a = 8.848(2) Å, b = 9.190(2) Å, c = 13.293(3) Å, β= 98.89(3)°, V = 1067.9(5) Å3, Z = 2. For 9, C18H15N10S2Re: monoclinic, P21, a = 8.796(2) Å, b = 9.008(2) Å, c = 13.208(3) Å, β= 97.90(3)°, V = 1036.6(5) Å3, Z = 2. For 12, C18H15N9S3Cl2Mo: monoclinic, P21/n, a = 10.52900(10) Å, b = 15.1116(3) Å, c = 15.8193(3) Å, β= 108.4790(10)°, V = 2387.23(7) Å3, Z = 4. Complexes 2 and 3 serve as models for the binding of Tc(V)-oxo and Re(V)-oxo species to hydrazinonicotinamide (HYNIC)-conjugated chemotactic peptides. Furthermore, since the use of the pyrimidinethiol coligand in the {99mTc-HYNIC-peptide} radiochemical species results in favorable pharmacokinetics, the thiolate derivatives 8 and 9 provide models for possible modes of interaction of metal-hydrazine cores with coligands in the radiopharmaceutical reagents.

Original languageEnglish (US)
Pages (from-to)2701-2716
Number of pages16
JournalInorganic Chemistry
Volume37
Issue number11
DOIs
StatePublished - 1998

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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