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.
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.
Rose
David J.
DJ
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.
Maresca
Kevin P.
KP
Nicholson
Terrence
T
Davison
Alan
A
Jones
Alun G.
AG
Babich
John
J
Fischman
Alan
A
Graham
Wendy
W
DeBord
Jeffery R. D.
JR
Zubieta
Jon
J