锝、铼和钼的具有{M(η(1)-H(x)NNR)(η(2)-H(y)NNR)}核心的有机肼基配合物的合成与表征及其与具有诊断应用的放射性标记有机肼衍生趋化肽的关系。
Synthesis and Characterization of Organohydrazino Complexes of Technetium, Rhenium, and Molybdenum with the {M(eta(1)-H(x)()NNR)(eta(2)-H(y)()NNR)} Core and Their Relationship to Radiolabeled Organohydrazine-Derivatized Chemotactic Peptides with Diagnostic Applications.
作者信息
Rose David J., Maresca Kevin P., Nicholson Terrence, Davison Alan, Jones Alun G., Babich John, Fischman Alan, Graham Wendy, DeBord Jeffery R. D., Zubieta Jon
机构信息
Department of Chemistry, Syracuse University, Syracuse, New York 13244, Chemistry Department, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, Department of Radiology, Harvard Medical School and Brigham and Women's Hospital, Boston, Massachusetts 02215, and Department of Radiology, Massachusetts General Hospital, Boston, Massachusetts 02214.
出版信息
Inorg Chem. 1998 Jun 1;37(11):2701-2716. doi: 10.1021/ic970352f.
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(eta(1)-NNC(5)H(4)NH(x)())(eta(2)-HNNH(y)()C(5)H(4)N)} core, represented by [TcCl(3)(NNC(5)H(4)NH)(HNNC(5)H(4)N)] (2), [ReCl(3)(NNC(5)H(4)NH)(HNNC(5)H(4)N)] (3), and [MoCl(3)(NNC(5)H(4)NH)(HNNHC(5)H(4)N)] (6). The reaction of 3 with NEt(3) results in the formation of [HNEt(3)][[ReCl(3)(NNC(5)H(4)N)(HNNC(5)H(4)N)].H(2)O (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 [ReCl(3)(NNC(3)H(4)N(2)H)(HNNHC(3)H(4)N(2)H)] (5). Reaction of 3 with pyridine-2-thiol and pyrimidine-2-thiol yields two structurally characterized derivatives with a modified {Re(eta(1)-NNC(5)H(4)N)(eta(2)-HNNC(5)H(4)N)} core, [Re(C(5)H(4)NS)(2)(NNC(5)H(4)N)(HNNC(5)H(4)N)] (8) and [Re(C(4)H(3)N(2)S)(2)(NNC(5)H(4)N)(HNNC(5)H(4)N)] (9), respectively. Reaction of 6 with pyrimidine-2-thiol led to the isolation of the analogous [Mo(C(4)H(3)N(2)S)(2)(NNC(5)H(4)N)(HNNHC(5)H(4)N)] (11) and the seven-coordinate monohydrazine core complex [Mo(C(4)H(3)N(2)S)(3)(NNC(5)H(4)N)].CH(2)Cl(2) (12). In similar fashion, the reaction of 2 with pyridine-2-thiol yielded a complex structurally analogous to 8, [Tc(C(5)H(4)NS)(2)(NNC(5)H(4)N)(HNNC(5)H(4)N)] (7). Crystal data for 3, C(10)H(10)Cl(3)N(6)Re: triclinic, P&onemacr;, a = 7.527(2) Å, b = 7.599(2) Å, c = 13.118(3) Å, alpha = 106.55(3) degrees, beta = 90.28(3) degrees, gamma = 93.83(3) degrees, V = 717.4(4) Å(3), Z = 2. For 4, C(16)H(27)Cl(3)N(7)ORe: orthorhombic, P2(1)2(1)2(1), a = 7.503(2) Å, b = 10.3643(2) Å, c = 30.1590(5) Å, V = 2345.20(6) Å(3), Z = 2. For 5, C(6)H(12)Cl(3)N(8)Re: monoclinic, P2(1)/n, a = 9.093(2) Å, b = 11.105(2) Å, c = 14.295(3) Å, beta = 94.71(3) degrees, V = 1438.6(7) Å(3), Z = 4. For 6, C(10)H(11)Cl(3)N(6)Mo: monoclinic, P2(1)/c, a = 15.366(3) Å, b = 7.804(2) Å, c = 12.378(3) Å, beta = 95.92(3) degrees, V = 1476.4(5) Å(3), Z = 4. For 7, C(20)H(17)N(8)S(2)Tc: monoclinic, P2(1), a = 8.827(2) Å, b = 9.278(2) Å, c = 13.304(3) Å, beta = 98.92(3) degrees, V = 1076.5(5) Å(3), Z = 2, 2564 reflections. For 8, C(20)H(17)N(8)S(2)Re: monoclinic, P2(1), a = 8.848(2) Å, b = 9.190(2) Å, c = 13.293(3) Å, beta = 98.89(3) degrees, V = 1067.9(5) Å(3), Z = 2. For 9, C(18)H(15)N(10)S(2)Re: monoclinic, P2(1), a = 8.796(2) Å, b = 9.008(2) Å, c = 13.208(3) Å, beta = 97.90(3) degrees, V = 1036.6(5) Å(3), Z = 2. For 12, C(18)H(15)N(9)S(3)Cl(2)Mo: monoclinic, P2(1)/n, a = 10.52900(10) Å, b = 15.1116(3) Å, c = 15.8193(3) Å, beta = 108.4790(10) degrees, V = 2387.23(7) Å(3), 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 {(99m)Tc-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.
在甲醇中用二盐酸2 - 肼基吡啶还原高铼酸盐、钼酸盐和高锝酸盐，已制备出一类含有{M(η(1)-NNC₅H₄NHₓ)(η(2)-HNNHᵧC₅H₄N)}核的配合物，以[TcCl₃(NNC₅H₄NH)(HNNC₅H₄N)] (2)、[ReCl₃(NNC₅H₄NH)(HNNC₅H₄N)] (3)和[MoCl₃(NNC₅H₄NH)(HNNHC₅H₄N)] (6)为代表。3与NEt₃反应通过吡啶氮位点的去质子化形成[HNEt₃][[ReCl₃(NNC₅H₄N)(HNNC₅H₄N)].H₂O (4)。类似地，用氢溴酸2 - 肼基 - 2 - 咪唑啉还原高铼酸盐已制备出类似的[ReCl₃(NNC₃H₄N₂H)(HNNHC₃H₄N₂H)] (5)。3与2 - 吡啶硫醇和2 - 嘧啶硫醇反应生成两种具有修饰的{Re(η(1)-NNC₅H₄N)(η(2)-HNNC₅H₄N)}核的结构表征衍生物，分别为[Re(C₅H₄NS)₂(NNC₅H₄N)(HNNC₅H₄N)] (8)和[Re(C₄H₃N₂S)₂(NNC₅H₄N)(HNNC₅H₄N)] (9)。6与2 - 嘧啶硫醇反应得到类似的[Mo(C₄H₃N₂S)₂(NNC₅H₄N)(HNNHC₅H₄N)] (11)和七配位单肼核配合物[Mo(C₄H₃N₂S)₃(NNC₅H₄N)].CH₂Cl₂ (12)。以类似方式，2与2 - 吡啶硫醇反应生成结构类似于8的配合物[Tc(C₅H₄NS)₂(NNC₅H₄N)(HNNC₅H₄N)] (7)。3的晶体数据，C₁₀H₁₀Cl₃N₆Re：三斜晶系，P&onemacr;，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) ų，Z = 2。4的晶体数据，C₁₆H₂₇Cl₃N₇ORe：正交晶系，P2(1)2(1)2(1)，a = 7.503(2) Å，b = 10.3643(2) Å，c = 30.1590(5) Å，V = 2345.20(6) ų，Z = 2。5的晶体数据，C₆H₁₂Cl₃N₈Re：单斜晶系，P2(1)/n，a = 9.093(2) Å，b = 11.105(2) Å，c = 14.295(3) Å，β = 94.71(3)°，V = 1438.6(7) ų，Z = 4。6的晶体数据，C₁₀H₁₁Cl₃N₆Mo：单斜晶系，P2(1)/c，a = 15.366(3) Å，b = 7.804(2) Å，c = 12.378(3) Å，β = 95.92(3)°，V = 1476.4(5) ų，Z = 4。7的晶体数据，C₂₀H₁₇N₈S₂Tc：单斜晶系，P2(1)，a = 8.827(2) Å，b = 9.278(2) Å，c = 13.304(3) Å，β = 98.92(3)°，V = 1076.5(5) ų，Z = 2，2564个反射。8的晶体数据，C₂₀H₁₇N₈S₂Re：单斜晶系，P2(1)，a = 8.848(2) Å，b = 9.190(2) Å，c = 13.293(3) Å，β = 98.89(3)°，V = 1067.9(5) ų，Z = 2。9的晶体数据，C₁₈H₁₅N₁₀S₂Re：单斜晶系，P2(1)，a = 8.796(2) Å，b = 9.008(2) Å，c = 13.208(3) Å，β = 97.90(3)°，V = 1036.6(5) ų，Z = 2。12的晶体数据，C₁₈H₁₅N₉S₃Cl₂Mo：单斜晶系，P2(1)/n，a = 10.52900(10) Å，b = 15.1116(3) Å，c = 15.8193(3) Å，β = 108.4790(10)°，V = 2387.23(7) ų，Z = 4。配合物2和3作为Tc(V)-氧代和Re(V)-氧代物种与肼基烟酰胺(HYNIC)共轭趋化肽结合的模型。此外，由于在{(⁹⁹ᵐTc - HYNIC - 肽)}放射性化学物种中使用嘧啶硫醇共配体导致良好的药代动力学，硫醇盐衍生物8和9为放射性药物试剂中金属 - 肼核与共配体可能的相互作用模式提供了模型。
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