Stereosensitive formation and interconversion of sulfur-bridged cobalt(III)–mercury(II) polynuclear complexes with d- and/or l-penicillaminates

Yamada, Yasunori; Hirano, A.; Fujita, Motomichi; Amir, Nagina; Miyashita, Yoshitaro; Okamoto, Ken‐ichi

doi:10.1016/j.ica.2004.09.032

Cited by 8 publications

(3 citation statements)

References 24 publications

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“…In D 2 O, 13 C NMR spectrum of 1b shows five signals due to the L-pen ligands and five signals characteristic for the coordinated bpy ligand [1][2][3][4][5][19][20][21]. The other monomeric optically active dinuclear complex cations, 2a, 2b, 3a, and 3b, exhibit similar ten signals due to the bpy and pen ligands, accompanied by additional signals ascribed as the carbon atoms of -CH 3 figure 3.…”

Section: Characterizationmentioning

confidence: 99%

Stereospecific interactions through π -conjugated systems of sulfur-bridged dinuclear Co(III)-Pd(II) and Co(III)-Pt(II) complexes of optically active penicillaminates

Yamada

Inoue

Okamoto

2008

Journal of Coordination Chemistry

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The reaction of trans(N)-[Co(D-pen) 2 ] À (pen ¼ penicillaminate) or trans(N)-[Co(L-pen) 2 ] À with [MCl 2 (L)] (M ¼ Pd or Pt, L ¼ 2,2 0 -bipyridine (bpy) or 4,4 0 -dimethyl-2,2 0 -bipyridine (dmbpy)) stereoselectively gave an optically active S-bridged dinuclear complex, [M(L){Co(Dpen) 2 }]Cl Á 3H 2 O or [M(L){Co(L-pen) 2 }]Cl Á 3H 2 O. The mixture of equimolar amounts of these two enantiomers in H 2 O crystallizes as [M(L){Co(D-pen) 2 }] 0.5 [M(L){Co(Lpen)in which the enantiomeric complex cations are included in the ratio of 1 : 1. In the crystals of 1cCl Á 7H 2 O, [Pd(bpy){Co(D-pen) 2 }] þ (1a) and [Pd(bpy){Co(L-pen) 2 }] þ (1b) are arranged alternately while overlapping the bpy planes along the a axis, and the electronic systems of bpy moieties interact with each other. This is quite a contrast to the optically active 1aCl Á 3H 2 O or 1bCl Á 3H 2 O, which exist as monomers without intermolecular interactions. In crystals of 2cCl Á 7H 2 O and 3cCl Á 6H 2 O, similarly, the two enantiomeric complex cations interact with each other through the dmbpy frameworks. However, the interplane distances between the stacked systems in these dmbpy complexes are considerably longer than in the bpy complexes. Such structural characteristics significantly reflect their diffuse reflectance spectra.

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Section: Characterizationmentioning

confidence: 99%

Stereospecific interactions through π -conjugated systems of sulfur-bridged dinuclear Co(III)-Pd(II) and Co(III)-Pt(II) complexes of optically active penicillaminates

Yamada

Inoue

Okamoto

2008

Journal of Coordination Chemistry

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“…In D 2 O, all the complexes exhibit 1 H NMR signals due to pen 2À and bpma in the region of 1.4-3.7 and 3.9-8.8, respectively [2][3][4][5][6][7][8]10]. Among these signals, the signals due to 6-and 6 0 -positions of pyridine protons (d = 8.64, and 8.70) are slightly resolved, reflecting that two pyridylmethyl frameworks in bpma are unequivalent to each other.…”

Section: Characterizationmentioning

confidence: 99%

“…Actually, an optically active mononuclear Co(III) complex, trans(N)-[Co(D-pen-N,O,S) 2 ] À , reacts a linear-type two coordinated Au(I) ion to form a chiral S-bridged hexanuclear complex, [Au 3 {Co(D-pen) 2 } 3 ] [1]. Similar reactions of trans(N)-[Co(D-pen) 2 ] À with Cd(II) and Hg(II) ions give trinuclear complexes, [Cd(OH 2 ){Co(D-pen) 2 } 2 ] and [Hg{Co(D-pen) 2 } 2 ], respectively [2,3]. In addition, the doubly S-bridged dinuclear complex, [M(bpy) {Co(D-pen) 2 }] + (M = Pd(II) or Pt(II), bpy = 2,2 0 -bipyridine), can be derived from the reaction with [MCl 2 (bpy)], in which the two Cl À ligands are susceptible to substitutions by other ligands [4].…”

Section: Introductionmentioning

confidence: 99%