Abstract:3 )] (3). The structure of 3 consists of distorted octahedral Re(V) monomers. The coordination geometry at the rhenium is defined by a terminal oxo-group, the nitrogen and sulfur donors of the chelating mercaptopyridine, the nitrogen and sulfur donors of a bidentate (Hhbma) 2− ligand, and the phosphorus of the PPh 3 group. The −C 6 H 4 OH arm of (Hhbma) 2− is pendant, and the coordinated nitrogen of this ligand is present as a deprotonated amido nitrogen.
“…Furthermore, the Re−N6 and Re−N7 bond lengths of 2.16(2) and 2.28(2) Å, respectively, illustrate the range of Re−N single bonds and permit an internal comparison with the Re−N1 and Re−N4 multiple bonds. The average Re−S distance for 5b is 2.39(1) Å, well within the range of other examples previously reported ( − ). 7 A view of the structure of 5 , showing the atom-labeling scheme and 50% thermal ellipsoids.…”
Hydrazinonicotinamide (HYNIC) forms stable coordination complexes with Tc-99m when reacted with Tc(V)oxo species such as Tc-mannitol or other Tc-polyhydric complexes. However, radio-HPLC of [Tc-For-MLFK-HYNIC] labeled via Tc-polyhydric ligands demonstrated multiple radiochemical species each with unique biodistribution patterns. This is likely due to the fact that Tc can bind to the hydrazino moiety, as well as polyhydric ligands, in a variety of coordination geometries. Tridentate ligands, such as bis(mercaptoethyl)methylamine (NS2), may constrain the possible coordination geometries and improve overall stability. To investigate this, we synthesized NS2, converted the [Tc-mannitol-For-MLFK-HYNIC] to the corresponding NS2-containing complex [Tc-NS2-For-MLFK-HYNIC], and compared its infection imaging and biodistribution properties with [Tc-mannitol-For-MLFK-HYNIC]. Conversion to the NS2 complex was confirmed by HPLC which showed a single unique hydrophobic species with retention time greater than the [Tc-mannitol-For-MLFK-HYNIC] complex. Imaging experiments with both preparations were performed in rabbits with E. coli infections in the left thigh. Tissue radioactivity measurements demonstrated that compared to Tc-mannitol-peptide, accumulation of Tc-NS2-peptide was lower in blood, heart, and normal muscle and higher in spleen, infected muscle, and pus (p < 0.01). These results indicate that the Tc-NS2-peptide complex is chemically more homogeneous and exhibits improved infection localization and biodistribution properties. In an effort to model the interactions of the metal-HYNIC core with NS2 and related ligand types, the reactions of [ReCl3(NNC5H4NH)(NHNC5H4N)] and [99TcCl3(NNC5H4NH)(NHNC5H4N)], effective structural analogues for the [M(NNC5H4NH(x))2] core, with NS2, C5H3N-2,6-(CH2SH)2, O(CH2CH2SH)2, and S(CH2CH2SH)2 were investigated and the compounds [M[CH3N(CH2CH2S)2](NNC5H4N)(NHNC5H4N] (M = 99Tc (5a), Re (5b)), [Re[C5H3N-2,6-(CH2S)2](NNC5H4N)(NHNC5H4N)].CH2Cl2.0.5MeOH (7), [Re[SCH2CH2)2O] (NNC5H4N)(NHNC5H4N)] (8), and [Re[(SCH2CH2)2S](NNC5H4NH)(NHNC5H4N)]Cl (9) were isolated. Similarly, the reaction of [ReCl3(NNC5H4NH)(NHNC5H4N)] with the bidentate ligands pyridine-2-methanethiol and 3-(trimethlysilyl)pyridine-2-thiol led to the isolation of [ReCl(C5H4N-2-CH2S) (NNC5H4N)(NHNC5H4N)] (10) and [Re(2-SC5H3N-3-SiMe3)2 (NNC5H4N)(NHNC5H4N)] (11), respectively, while reaction with N-methylimidazole-2-thiol yielded the binuclear complex [Re(OH)Cl(SC3H2N2CH3)2(NNC5H4N)2 (NHNC5H4N)2] (12). The analogous metal-(HYNIC-OH) precursor, [ReCl3[NNC5H3NH(CO2R)] [NHNC5H3N(CO2R)]] (R = H, 13a; R = CH3, 13b) has been prepared and coupled to lysine to provide [RCl3[NNC5H3NH(CONHCH2CH2CH2CH2CH(NH2)CO2H)] [NHNC5H3NH(CONHCH2CH2CH2CH2CH(NH2)CO2H)]].2HCl (14.2HCl), while the reaction of the methyl ester 13b with 2-mercaptopyridine yields [Re(2-SC5H4N)2[NNC5H3N(CO2Me)][NHNC5H3N(CO2Me)]] (15). While the chemical studies confirm the robustness of the M-HYNIC core (M = Tc, Re) and its persistence in ligand substitution reactions at adjacen...
“…Furthermore, the Re−N6 and Re−N7 bond lengths of 2.16(2) and 2.28(2) Å, respectively, illustrate the range of Re−N single bonds and permit an internal comparison with the Re−N1 and Re−N4 multiple bonds. The average Re−S distance for 5b is 2.39(1) Å, well within the range of other examples previously reported ( − ). 7 A view of the structure of 5 , showing the atom-labeling scheme and 50% thermal ellipsoids.…”
Hydrazinonicotinamide (HYNIC) forms stable coordination complexes with Tc-99m when reacted with Tc(V)oxo species such as Tc-mannitol or other Tc-polyhydric complexes. However, radio-HPLC of [Tc-For-MLFK-HYNIC] labeled via Tc-polyhydric ligands demonstrated multiple radiochemical species each with unique biodistribution patterns. This is likely due to the fact that Tc can bind to the hydrazino moiety, as well as polyhydric ligands, in a variety of coordination geometries. Tridentate ligands, such as bis(mercaptoethyl)methylamine (NS2), may constrain the possible coordination geometries and improve overall stability. To investigate this, we synthesized NS2, converted the [Tc-mannitol-For-MLFK-HYNIC] to the corresponding NS2-containing complex [Tc-NS2-For-MLFK-HYNIC], and compared its infection imaging and biodistribution properties with [Tc-mannitol-For-MLFK-HYNIC]. Conversion to the NS2 complex was confirmed by HPLC which showed a single unique hydrophobic species with retention time greater than the [Tc-mannitol-For-MLFK-HYNIC] complex. Imaging experiments with both preparations were performed in rabbits with E. coli infections in the left thigh. Tissue radioactivity measurements demonstrated that compared to Tc-mannitol-peptide, accumulation of Tc-NS2-peptide was lower in blood, heart, and normal muscle and higher in spleen, infected muscle, and pus (p < 0.01). These results indicate that the Tc-NS2-peptide complex is chemically more homogeneous and exhibits improved infection localization and biodistribution properties. In an effort to model the interactions of the metal-HYNIC core with NS2 and related ligand types, the reactions of [ReCl3(NNC5H4NH)(NHNC5H4N)] and [99TcCl3(NNC5H4NH)(NHNC5H4N)], effective structural analogues for the [M(NNC5H4NH(x))2] core, with NS2, C5H3N-2,6-(CH2SH)2, O(CH2CH2SH)2, and S(CH2CH2SH)2 were investigated and the compounds [M[CH3N(CH2CH2S)2](NNC5H4N)(NHNC5H4N] (M = 99Tc (5a), Re (5b)), [Re[C5H3N-2,6-(CH2S)2](NNC5H4N)(NHNC5H4N)].CH2Cl2.0.5MeOH (7), [Re[SCH2CH2)2O] (NNC5H4N)(NHNC5H4N)] (8), and [Re[(SCH2CH2)2S](NNC5H4NH)(NHNC5H4N)]Cl (9) were isolated. Similarly, the reaction of [ReCl3(NNC5H4NH)(NHNC5H4N)] with the bidentate ligands pyridine-2-methanethiol and 3-(trimethlysilyl)pyridine-2-thiol led to the isolation of [ReCl(C5H4N-2-CH2S) (NNC5H4N)(NHNC5H4N)] (10) and [Re(2-SC5H3N-3-SiMe3)2 (NNC5H4N)(NHNC5H4N)] (11), respectively, while reaction with N-methylimidazole-2-thiol yielded the binuclear complex [Re(OH)Cl(SC3H2N2CH3)2(NNC5H4N)2 (NHNC5H4N)2] (12). The analogous metal-(HYNIC-OH) precursor, [ReCl3[NNC5H3NH(CO2R)] [NHNC5H3N(CO2R)]] (R = H, 13a; R = CH3, 13b) has been prepared and coupled to lysine to provide [RCl3[NNC5H3NH(CONHCH2CH2CH2CH2CH(NH2)CO2H)] [NHNC5H3NH(CONHCH2CH2CH2CH2CH(NH2)CO2H)]].2HCl (14.2HCl), while the reaction of the methyl ester 13b with 2-mercaptopyridine yields [Re(2-SC5H4N)2[NNC5H3N(CO2Me)][NHNC5H3N(CO2Me)]] (15). While the chemical studies confirm the robustness of the M-HYNIC core (M = Tc, Re) and its persistence in ligand substitution reactions at adjacen...
The syntheses and structural characterizations of a series of novel '3+2' and '2+2+1' mixed-ligand complexes carrying 8-hydroxy-5-nitroquinoline (HL) as the bidentate N,O donor atom system are reported. Thus one-pot reactions of [ReOCl(3)(PPh(3))(2)] with dianionic tridentate ligands H(2)L(n) (where H(2)L(1)=HOC(6)H(4)-2-CH=NC(6)H(4)-2-OH; H(2)L(2)=HOC(6)H(4)-2-CH=N-C(6)H(4)-2-SH; H(2)L(3)=HOC(6)H(4)-2-CH=NN=C(NHC(6)H(5))-SH; H(2)L(4)=2-CH(2)OH-C(5)H(3)N-6-CH(2)SH; and H(2)L(5)=2-CO(2)H-C(5)H(3)N-6-CO(2)H) and HL afforded a series of '3+2' oxorhenium complexes of the type [ReO(H(2)L(n))(L)] 2-6, which exhibit distorted octahedral geometries. Crystals of 1 are monoclinic space group C2/c, a=16.702(1), b=14.275(1), c=22.363(2) A, beta=108.083(1) degrees V=5068.2(7) A(beta) and Z=8; those of 2 are monoclinic space group P2(1)/n, a=8.5093(4) b=38.518(2), c=11.6092(5) A, beta=97.708(1) degrees , V=3770.7(3) A(3) and Z=8; those of 5 are triclinic, space group P1-, a=7.5899(8), b=10.322(1), c=11.905(1) A, alpha=78.636(2) degrees , beta=74.229(2) degrees , gamma=71.391(2) degrees , V=844.3(2) A(3), and Z=2. Upon reaction of 2,6-pyridinedimethanol (H(2)L(6)) with the intermediate complex [ReOCl(2)(L)(PPh(3))] (1), only one of the two methylene hydroxy group was deprotonated and a new '2+2+1' complex [ReO(OCH(3))(HL(6))(L)].CH(3)OH (7) was obtained. Crystal data for 7: monoclinic P2(1)/n, a=12.0579(6), b=11.0993(6), c=14.9262(8) A, beta=107.872(1) degrees , V=1901.2(2) A(3), and Z=8. In the preparation of complex 3, cleavage of the C=N bond of the Schiff base H(2)L(2) was observed and the '2+2+1' complex 8 [ReO(PPh(3))(eta(2)-NHC(6)H(4)-2-S)(L)].CH(2)Cl(2) having 2-aminothiophenol as a dianionic bidentate ligand was isolated. Crystals of 8 are monoclinic space group C2/c, a=25.627(2), b=8.1305(6) c=31.404(2) A beta=96.147(1) degrees , V=6505.7(8) A(3), and Z=8. Reduction of HL to 8-hydroxy-5-aminoquinoline was realized during the formation of complex 6, and a new complex 9 was thus isolated involving the coordination of two sets of N,O donor atoms from L and 8-hydroxy-5-aminoquinoline while a methoxy oxygen atom completes the octahedral coordination geometry. Crystals of 9 are monoclinic space group P2(1)/n, a=7.5330(6), b=15.095(1), c=16.394(1) A, beta=99.690(2) degrees , V=1837.7(3) A(3), and Z=4.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
