Penicillamin‐Komplexe des Nickels, Chroms und Molybdäns — Strukturelle Besonderheiten und biologische/medizinische Relevanz

Abstract

Die Verbindungen Tl2[NiII(H2O)6][NiII(D‐Pen)(L‐Pen)]2[NiII(SCN)2(H2O)4] 1, Tl[NiII(D‐Pen)2H] · H2O 2, Tl[CrIII(D‐Pen)2] 3 und Na2[Mo 2VO4(Pen)2] · 3 CH3OH · 3 H2O 4 wurden durch Umsetzung von Nickelnitrat (für 1), Nickelacetat (für 2), Kaliumchromat (für 3) und Natriummolybdat (für 4) mit D‐ bzw. D, L‐Penicillamin in wäßriger Lösung dargestellt und durch Einkristallstrukturanalyse und andere physikalische Methoden charakterisiert. Während in den Ni‐Pen‐Komplexen von 1 und 2 Penicillamin als zweizähniger Ligand (N, S) fungiert, sind CrIII in 3 und MoV in 4 über N, O und S koordiniert. Bemerkenswert ist, daß in 1 drei verschiedene Ni‐Komplexe und zwar ein kationischer, ein neutraler und ein anionischer in einer Elementarzelle vorliegen. 1: C2/m, a = 1 484,6(4), b = 1 358,7(4), c = 1 204,7(3) pm, β = 103,75(2)°, V = 2 360,4(11) ° 106 pm3, R = 0,042 für 1 633 unabhängige Reflexe (Fo> 4,0σ(Fo)), Z = 2. 2: C2, a = 2 279,9(7), b = 613,1(1), c = 1 275,2(3) pm, β = 110,94(2)°, V = 1 664,8(6) · 106 pm3, R = 0,056 für 1 413 unabhängige Reflexe (Fo> 4,0σ(Fo)), Z = 4. 3: C2, a = 2 054,0(3), b = 592,1(1), c = 606,7(1) pm, β = 92,89(1)°, V = 736,95(17) · 106 pm3, R = 0,028 für 862 unabhängige Reflexe (Fo> 4,0σ(Fo)), Z = 2. 4: P1, a = 996,2(4), b = 1 222,2(7), c = 1 395,3(7) pm, = 114,27(4), β = 104,55(4), γ = 95,63(4)°, V = 1 459,4(13) · 106 pm3, R = 0,072 für 3 763 unabhängige Reflexe (Fo> 4,0σ(Fo)), Z = 2.

Lanthanide complexes of D-penicillamine: formation constants, spectral and thermal properties

“…D-penicillamine, together with its zwitterionic form, with three functional groups (-NH 2 , -S 2À and -COO À ) usually forms bidentate complexes by coordination of N and S atoms [7,8], but formation of monodentate (S) [9,10], tridentate (N,O,S,) or tetradentate (N,O,O,S) complexes [11,12] cannot be ruled out. The sulfur, nitrogen or oxygen atoms could also act as a bridging ligand [13].…”

Rational creation of chiral multinuclear and metallosupramolecular compounds from thiol-containing amino acids

“…Penicillamine is a thiol-containing amino acid, analogous to cysteine, and has been used as a multidentate organic ligand, which can bind to a variety of metal centers through amine, carboxylate, and/or thiolate groups (Chart 1). [26][27][28][29][30][31][32][33][34][35] Despite the structural similarity of penicillamine to cysteine, except the presence of two methyl groups on the b-carbon atom, its chiral configuration in to an [M V O] 3+ core in mixed tridentate-N,O,S and bidentate-N,S modes. 30,31 Thus, penicillamine usually acts as a tridentate-N,O,S or bidentate-N,S ligand toward an octahedral metal center, although we have recently found that D-Hpen coordinates to a [Ru II (bpy) 2 ] 2+ core in a bidentate-O,S mode to form [Ru(bpy) 2 (D-Hpen-O,S)] + that is thermally converted to [Ru II (bpy) 2 (D-Hpen-N,S)] + .…”

A Multinuclear Coordination System of L‐Cysteine and L‐Penicillamine That Induce Opposite Chiralities at Metal Centers

“…[13][14][15][16][17][18][19][20][21][22][23][24][25][26] Although a difference in coordination behavior between cysteine and penicillamine toward a given metal ion has been observed in some cases, [18,19] dpenicillamine commonly induces a chiral effect at a metal center opposite to that induced by l-cysteine, [20][21][22][23][24][25][26] which is consistent with their opposite d and l configurations. [13][14][15][16][17][18][19][20][21][22][23][24][25][26] Although a difference in coordination behavior between cysteine and penicillamine toward a given metal ion has been observed in some cases, [18,19] dpenicillamine commonly induces a chiral effect at a metal center opposite to that induced by l-cysteine, [20][21][22][23][24][25][26] which is consistent with their opposite d and l configurations.…”