Bifunctional Single Amino Acid Chelates for Labeling of Biomolecules with the {Tc(CO)3}+and {Re(CO)3}+Cores. Crystal and Molecular Structures of [ReBr(CO)3(H2NCH2C5H4N)], [Re(CO)3{(C5H4NCH2)2NH}]Br, [Re(CO)3{(C5H4NCH2)2NCH2CO2H}]Br, [Re(CO)3{X(Y)NCH2CO2CH2CH3}]Br (X = Y = 2-pyridylmethyl; X = 2-pyridylmethyl, Y = 2-(1-methylimidazolyl)methyl; X = Y = 2-(1-methylimidazolyl)methyl), [ReBr(CO)3{(C5H4NCH2)NH(CH2C4H3S)}], and [Re(CO)3{(C5H4NCH2)N(CH2C4H3S)(CH2CO2)}] Academic Article uri icon

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abstract

  • The reactions of a series of potentially tridentate ligands, derived from single amino acids or amino acid analogues, with [NEt(4)](2)[ReBr(3)(CO)(3)] have been investigated. The model compounds [Re(CO)(3)Br[(2-pyridylmethyl)NH(2)]] (1) and [Re(CO)(3)[(2-pyridylmethyl)(2)NH]]Br (2) were also prepared and structurally characterized. With ligands possessing two pyridyl appendages, (2-pyridylmethyl)(2)NX (X = -CH(2)CO(2)H, -CH(2)CO(2)Et, -CH(2)CH(2)CO(2)H, -CH(2)CH(2)CO(2)Et, -CH(2)CH(2)CH(2)CH(2)CH(NHCO(2)(t)Bu)CO(2)H), complexes of the type [Re(CO)(3)(ligand)]Br (3-6) were isolated. All possess the fac-[Re(CO)(3)N(3)] coordination geometry in the cationic molecular unit. Similarly, the ligands with the imidazolyl arms (2-pyridylmethyl)[2-(1-methylimidazolyl)methyl]NCH(2)CO(2)Et and [2-(1-methylimidazolyl)methyl](2)NCH(2)CO(2)Et, complexes 7 and 8 of the same [Re(CO)(3)(ligand)]Br type, were prepared. Replacement of one pyridyl arm with a thiophene group yielded the complex [Re(CO)(3)[(2-pyridylmethyl)N(CH(2)CO(2))(2-thiophenemethyl)]] (9), while additional substitution of X = -H for -CH(2)CO(2)H yielded [Re(CO)(3)Br[(2-pyridylmethyl)NH(2-thiophenemethyl)]] (10). In both 9 and 10, the thiophene is uncoordinated and pendant, and the derivatives display fac-[Re(CO)(3)N(2)O] and fac-[Re(CO)(3)N(2)Br] coordination geometries, respectively. Crystal data: C(9)H(8)BrN(2)O(3)Re (1), triclinic P1, a = 8.156(1) A, b = 12.077(1) A, c = 12.945(2) A, alpha = 92.183(3) degrees, beta = 107.848(3) degrees, gamma = 100.955(7) degrees, V = 1185.1(3) A, Z = 4; C(15)H(13)BrN(3)O(3)Re (2), tetragonal P4(1), a = 8.6095(3) A, c = 22.228(1) A, V = 1646.9(1) A(3), Z = 4; C(17)H(14)BrN(3)O(5)Re.CH(3)OH (3), monoclinic P2(1)/m, a = 7.4425(3) A, b = 9.7596(4) A, c = 14.0646(6) A, beta = 97.753(1) degrees, V = 1012.26(7) A(3), Z = 2; C(19)H(19)BrN(3)O(5)Re (4), tetragonal P42(1)c, a = 16.895(3) A, c = 15.042(3) A, V = 4293.7(13) A(3), Z = 8; C(18)H(20)BrN(4)O(5)Re.CH(3)OH.H(2)O (7), monoclinic P2(1)/c, a = 10.2816(4) A, b = 30.386(1) A, c = 14.5810(6) A, beta = 99.868(1) degrees, V = 4488.03(3) A(3), Z = 8; C(17)H(21)BrN(5)O(5)Re.0.5CH(2)Cl(2).0.5H(2)O (8), triclinic P1, a = 11.5363(6) A, b = 13.1898(6) A, c = 16.4933(8) A, alpha = 89.356(1) degrees, beta = 74.907(1) degrees, gamma = 76.216(1) degrees, V = 2349.8(2) A(3), Z = 4; C(16)H(13)N(2)O(5)ReS (9), monoclinic P2(1)/c, a = 17.2072(7) A, b = 8.5853(4) A, c = 11.5607(5) A, beta = 101.73(1) degrees, V = 1672.2(1) A(3), Z = 4; and C(14)H(12)N(2)O(3)BrReS (10), triclinic P1, a = 7.5585(3) A, b = 9.7713(4) A, c = 11.7103(4) A, alpha = 109.566(1) degrees, beta = 98.298(1) degrees, gamma = 100.925(1) degrees, V = 779.73(5) A(3), Z = 2.

authors

  • Banerjee, Sangeeta Ray
  • Levadala, Murali K
  • Lazarova, Neva
  • Wei, Lihui
  • Valliant, John F
  • Stephenson, Karin A
  • Babich, John W
  • Maresca, Kevin P
  • Zubieta, Jon

publication date

  • December 2002