Synthesis, Characterization, and Chiral Behavior of S-Bridged CoIIIPtIICoIII Trinuclear Complexes Composed of Bis(thiolato)-Type Octahedral Units cis(S)-[Co(aet)2(en)]+ and/or trans(N)-[Co(<scp>d</scp>-pen- N,O,S)2]- (aet = 2-Aminoethanethiolate, <scp>d</scp>-pen = <scp>d</scp>-Penicillaminate)

Honda, Hirokazu; Yoshimura, Takashi; Hirotsu, Masakazu; Kawamoto, Tatsuya; Konno, Takumi

doi:10.1021/ic010696c

Cited by 18 publications

(17 citation statements)

References 43 publications

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“…3 3). 16 The dihedral angle between the Pt1S1S2 and Pt1S4S5 planes in (−) 3 CD 30 -[2a] 2+ is 5.6°, which is much smaller than that in DD/KK-[Pt{Co(aet) 2 (en)} 2 ] 4+ (13.1°).…”

Section: Synthesis and Characterization Of [Pt{co(aet) 3 } 2 ] 2+ ([2...mentioning

confidence: 96%

“…Noteworthy here is that both the racemic (DD/KK) and meso (DK) forms have been formed for [Pt{Co(aet) 2 (en)} 2 ] 4+ , which has been explained by the inertness of Pt-S bonds. 16 One may assume that the Pt-S bonds in the Co III Pt II Co III structure are weakened by the replacement of the terminal en ligands in [Pt{Co(aet) 2 (en)} 2 ] 4+ by aet ligands, allowing the intermolecular exchange of the [Co(aet) 3 ] units to form the more stable racemic form. However, the Pt-S bond distances in KK-[2a] 2+ and KK/DD-[2b] 2+ are quite similar to those in DD/KKand DK-[Pt{Co(aet) 2 (en)} 2 ] 4+ .…”

Section: Stereochemical Propertiesmentioning

confidence: 99%

“…However, the Pt-S bond distances in KK-[2a] 2+ and KK/DD-[2b] 2+ are quite similar to those in DD/KKand DK-[Pt{Co(aet) 2 (en)} 2 ] 4+ . 16 Thus, the difference in stereochemistry between [Pt{Co(aet) 2 (en)} 2 ] 4+ and [Pt{Co(aet) 3 } 2 ] 2+ ([2] 2+ ) seems to be ascribed to the difference in the stability of [Co(aet) 2 (L)] + or 0 (L = en, aet) towards isomerization. That is, fac(S)-[Co(aet) 3 ] could suffer isomerization to mer(S) so as to generate the more stable racemic form, while the C 2 -cis(S) geometry of [Co(aet) 2 (en)] + is retained in the course of the reaction with Pt II .…”

Section: Stereochemical Propertiesmentioning

confidence: 99%

“…That is, fac(S)-[Co(aet) 3 ] could suffer isomerization to mer(S) so as to generate the more stable racemic form, while the C 2 -cis(S) geometry of [Co(aet) 2 (en)] + is retained in the course of the reaction with Pt II . 16 Since syn- [2] 2+ ([2a] 2+ ) exists as a racemic (DD/KK) form, the linkage of two moles of syn- [2] 2+ with linear Au I ions is considered to give the meso (DDKK) form, besides the racemic (DDDD/KKKK) form. However, only the racemic form was produced for [Au 2 {Pt[Co(aet) 3 ] 2 } 2 ] 6+ ([3] 6+ ), as has been recognized for [M 2 {Pd[Co(aet) 3 ] 2 } 2 ] 6+ (M = Au I , Ag I ).…”

Section: Stereochemical Propertiesmentioning

confidence: 99%

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Synthesis, characterization, and stereochemistry of S-bridged CoIIIMCoIII(M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: building blocks for the construction of chiral heterometallic aggregates

et al. 2004

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The reaction of fac(S)-[Co(aet)(3)](aet = aminoethanethiolate) with [PdCl(4)](2-) in a 2:1 ratio in water gave an S-bridged Co(III)Pd(II)Co(III) trinuclear complex composed of two mer(S)-[Co(aet)(3)] units, [Pd[Co(aet)(3)](2)](2+)([1](2+)). In [1](2+), each of the two mer(S)-[Co(aet)(3)] units is bound to a square-planar Pd(II) ion through two of three thiolato groups, leaving two non-bridging thiolato groups at the terminal. Of two geometrical forms, syn and anti, possible for [Pd[Co(aet)(3)](2)](2+), which arise from the difference in arrangement of two terminal non-bridging thiolato groups, [1](2+) afforded only the syn form. A similar reaction of fac(S)-[Co(aet)(3)] with [PtCl(4)](2-) or trans-[PtCl(2)(NH(3))(2)] produced an analogous Co(III)Pt(II)Co(III) trinuclear complex, [Pt[Co(aet)(3)](2)](2+)([2](2+)), but both the syn and anti forms were formed for [2](2+). Complexes [1](2+) and syn- and anti-[2](2+), which exclusively exist as a racemic(DeltaDelta/LambdaLambda) form, were successfully optically resolved with use of [Sb(2)(R,R-tartrato)(2)](2-) as the resolving agent. The reaction of syn-[2](2+) with [AuCl[S(CH(2)CH(2)OH)(2)]] led to the formation of an S-bridged Co(III)(4)Pt(II)(2)Au(I)(2) octanuclear metallacycle, [Au(2)[Pt[Co(aet)(3)](2)](2)](6+)([3](6+)), while the corresponding reaction of anti-[2](2+) afforded a different product ([[4](3+)](n)) that is assumed to have a polymeric structure in [[Au[Pt[Co(aet)(3)](2)]](3+)](n).

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“…3 3). 16 The dihedral angle between the Pt1S1S2 and Pt1S4S5 planes in (−) 3 CD 30 -[2a] 2+ is 5.6°, which is much smaller than that in DD/KK-[Pt{Co(aet) 2 (en)} 2 ] 4+ (13.1°).…”

Section: Synthesis and Characterization Of [Pt{co(aet) 3 } 2 ] 2+ ([2...mentioning

confidence: 96%

Section: Stereochemical Propertiesmentioning

confidence: 99%

Section: Stereochemical Propertiesmentioning

confidence: 99%

Section: Stereochemical Propertiesmentioning

confidence: 99%

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Synthesis, characterization, and stereochemistry of S-bridged CoIIIMCoIII(M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: building blocks for the construction of chiral heterometallic aggregates

et al. 2004

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“…Since the establishment of Werner's coordination theory by his pioneering research on the optical resolution of chiral cobalt(III) complexes, chirality has been one of the most important and fascinating subject in coordination chemistry. During the past decade, much attention has been drawn to this subject in the field of coordination stereochemistry, associated with the growing interest in the design and creation of well-organized polynuclear and metallo-supramolecular species, the overall structures of which can be controlled by chirality of their building units. , Our research interest has been directed toward this subject, based on tris(chelate)-type cobalt(III) complexes with simple aminothiolate ligands such as 2-aminoethanethiolate (aet) and l -cysteinate ( l -cys), which are linked by transition metal ions to form a variety of S-bridged polynuclear and polymeric structures. − …”

Section: Introductionmentioning

confidence: 99%

Sulfur-Bridged Co^IIIPt^IICo^III Trinuclear Complexes with Mixed Aliphatic and Aromatic Thiolate Ligands: Effect of Nonbridging Ligands on the Homochiral Linkage of Cobalt(III) Octahedrons by Platinum(II)

et al. 2004

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The reaction of [Ni[Co(aet)(2)(pyt)](2)](2+) (aet = 2-aminoethanethiolate, pyt = 2-pyridinethiolate) with [PtCl(4)](2)(-) gave an S-bridged Co(III)Pt(II)Co(III) trinuclear complex composed of two [Co(aet)(2)(pyt)] units, [Pt[Co(aet)(2)(pyt)](2)](2+) ([1](2+)). When a 1:1 mixture of [Ni[Co(aet)(2)(pyt)](2)](2+) and [Ni[Co(aet)(2)(en)](2)](4+) was reacted with [PtCl(4)](2)(-), a mixed-type S-bridged Co(III)Pt(II)Co(III) complex composed of one [Co(aet)(2)(pyt)] and one [Co(aet)(2)(en)](+) units, [Pt[Co(aet)(2)(en)][Co(aet)(2)(pyt)]](3+) ([2](3+)), was produced, together with [1](2+) and [Pt[Co(aet)(2)(en)](2)](4+). The corresponding Co(III)Pt(II)Co(III) trinuclear complexes containing pymt (2-pyrimidinethiolate), [Pt[Co(aet)(2)(pymt)](2)](2+) ([3](2+)) and [Pt[Co(aet)(2)(en)][Co(aet)(2)(pymt)]](3+) ([4](3+)), were also obtained by similar reactions, using [Ni[Co(aet)(2)(pymt)](2)](2+) instead of [Ni[Co(aet)(2)(pyt)](2)](2+). While [Pt[Co(aet)(2)(en)](2)](4+) formed both the deltalambda (meso) and deltadelta/lambdalambda (racemic) forms in a ratio of ca. 1:1, the preferential formation of the deltadelta/lambdalambda form was observed for [1](2+) (ca. deltalambda:deltadelta/lambdalambda = 1:3) and [2](3+) (ca. delta(en)lambda(pyt)/lambda(en)delta(pyt):deltadelta/lambdalambda = 1:2). Furthermore, [3](2+) and [4](3+) predominantly formed the deltadelta/lambdalambda form. These results indicate that the homochiral selectivity for the S-bridged Co(III)Pt(II)Co(III) trinuclear complexes composed of two octahedral [Co(aet)(2)(L)](0 or +) units is enhanced in the order L = en < pyt < pymt. The isomers produced were separated and optically resolved, and the crystal structures of the meso-type deltalambda-[1]Cl(2).4H(2)O and the spontaneously resolved deltadelta-[4](ClO(4))(3).H(2)O were determined by X-ray analyses. In deltalambda-[1](2+), the delta and Lambda configurational mer(S).trans(N(aet))-[Co(aet)(2)(pyt)] units are linked by a square-planar Pt(II) ion through four aet S atoms to form a linear-type S-bridged trinuclear structure. In deltadelta-[4](3+), a similar linear-type trinuclear structure is constructed from the delta-mer(S).trans(N(aet))-[Co(aet)(2)(pymt)] and delta-C(2)-cis(S)-[Co(aet)(2)(en)](+) units that are bound by a Pt(II) ion with a slightly distorted square-planar geometry through four aet S atoms.

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A New Class of Hydroxo‐Bridged Heptacopper(II) Clusters with an Acentrosymmetric Corner‐Sharing Double‐Cubane Framework Supported by D‐Penicillaminedisulfides

Igashira‐Kamiyama

Fujioka

Mitsunaga

et al. 2008

Chemistry A European J

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Synthesis, Characterization, and Chiral Behavior of S-Bridged Co^IIIPt^IICo^III Trinuclear Complexes Composed of Bis(thiolato)-Type Octahedral Units cis(S)-[Co(aet)₂(en)]⁺ and/or trans(N)-[Co(d-pen- N,O,S)₂]^- (aet = 2-Aminoethanethiolate, d-pen = d-Penicillaminate)

Cited by 18 publications

References 43 publications

Synthesis, characterization, and stereochemistry of S-bridged CoIIIMCoIII(M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: building blocks for the construction of chiral heterometallic aggregates

Synthesis, characterization, and stereochemistry of S-bridged CoIIIMCoIII(M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: building blocks for the construction of chiral heterometallic aggregates

Sulfur-Bridged Co^IIIPt^IICo^III Trinuclear Complexes with Mixed Aliphatic and Aromatic Thiolate Ligands: Effect of Nonbridging Ligands on the Homochiral Linkage of Cobalt(III) Octahedrons by Platinum(II)

A New Class of Hydroxo‐Bridged Heptacopper(II) Clusters with an Acentrosymmetric Corner‐Sharing Double‐Cubane Framework Supported by D‐Penicillaminedisulfides

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Synthesis, Characterization, and Chiral Behavior of S-Bridged CoIIIPtIICoIII Trinuclear Complexes Composed of Bis(thiolato)-Type Octahedral Units cis(S)-[Co(aet)2(en)]+ and/or trans(N)-[Co(d-pen- N,O,S)2]- (aet = 2-Aminoethanethiolate, d-pen = d-Penicillaminate)

Cited by 18 publications

References 43 publications

Synthesis, characterization, and stereochemistry of S-bridged CoIIIMCoIII(M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: building blocks for the construction of chiral heterometallic aggregates

Synthesis, characterization, and stereochemistry of S-bridged CoIIIMCoIII(M = PdII, PtII) trinuclear complexes containing two non-bridging thiolato groups: building blocks for the construction of chiral heterometallic aggregates

Sulfur-Bridged CoIIIPtIICoIII Trinuclear Complexes with Mixed Aliphatic and Aromatic Thiolate Ligands: Effect of Nonbridging Ligands on the Homochiral Linkage of Cobalt(III) Octahedrons by Platinum(II)

A New Class of Hydroxo‐Bridged Heptacopper(II) Clusters with an Acentrosymmetric Corner‐Sharing Double‐Cubane Framework Supported by D‐Penicillaminedisulfides

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Synthesis, Characterization, and Chiral Behavior of S-Bridged Co^IIIPt^IICo^III Trinuclear Complexes Composed of Bis(thiolato)-Type Octahedral Units cis(S)-[Co(aet)₂(en)]⁺ and/or trans(N)-[Co(d-pen- N,O,S)₂]^- (aet = 2-Aminoethanethiolate, d-pen = d-Penicillaminate)

Sulfur-Bridged Co^IIIPt^IICo^III Trinuclear Complexes with Mixed Aliphatic and Aromatic Thiolate Ligands: Effect of Nonbridging Ligands on the Homochiral Linkage of Cobalt(III) Octahedrons by Platinum(II)