Synthesis and some properties of T-cage type CoIII4HgII4 and RhIII4HgII4 octanuclear complexes with 2-aminoethanethiolate

Kageyama, Y; Konno, Takumi; Okamoto, Ken‐ichi; Hidaka, Jinsai

doi:10.1016/0020-1693(95)04709-3

Cited by 20 publications

(4 citation statements)

References 12 publications

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“…80 mV at a scan rate of 100 mV s -1 . Similar redox behavior has been characteristically observed for [M 4 O{Co(aet) 3 } 4 ] 6+ (M = Zn II , E °‘ = −0.40, −0.52, −0.65, and −0.83 V; M = Hg II , E °‘ = −0.47, −0.58, −0.72, and −0.90 V) having a T -symmetrical S-bridged Co III 4 M 4 octanuclear structure. , These results imply that the T -symmetrical octanuclear structure observed in the crystal is retained in solution. [ 2 ] 6+ was optically resolved into its enantiomers, (+) and (−) , by SP-Sephadex C-25 column chromatography.…”

Section: Resultssupporting

confidence: 81%

“…The aqueous solution of [ 3 ] changes its color from green-blue to brown after several days at room temperature, which implies that [ 3 ] is not so stable in solution. A similar trend has been noticed for the mononuclear fac -[Co(aet) 3 ] and fac -[Co( l -cys- N , S ) 3 ] 3- . , However, the absorption spectral change with time for [ 3 ] was found to be considerably slower than that for fac -[Co(aet) 3 ]. That is, the absorption peak of the sulfur-to-cobalt CT band (269 nm) for [ 3 ] decreased only 1% in intensity for 1 h, while a 19% decrease of the corresponding band (274 nm) was observed for fac -[Co(aet) 3 ].…”

Section: Resultssupporting

confidence: 73%

“…Coordinated thiolato S atoms in mononuclear Co III complexes tend to bind with other metal ions to form S-bridged polynuclear structures. − In fact, a number of S-bridged polynuclear complexes composed of fac -[Co(thiolato- S ) 3 (amine- N ) 3 ]-type units have been prepared by the reactions of fac -[Co(aet) 3 ] or fac ( S )-[Co( l -cys- N,S ) 3 ] 3- (aet = 2-aminoethanethiolate; l -cys = l -cysteinate) with a variety of metal ions. − It has been pointed out that the structures of these polynuclear complexes are highly dependent on the properties of metal ions incorporated with fac -[Co(aet or l -cys- N , S ) 3 ] 0 or 3- . For example, the reaction of fac -[Co(aet) 3 ] with Zn 2+ gave an S-bridged Co III 4 Zn II 4 octanuclear complex, [Zn 4 O{Co(aet) 3 } 4 ] 6+ , while the reaction with Ag + produced an S-bridged Co III 2 Ag I 3 pentanuclear complex, [Ag 3 {Co(aet) 3 } 2 ] 3+ .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Chiral Properties of Co^III₂Ag^I₃ Pentanuclear, Co^III₄Zn^II₄ Octanuclear, and Co^III Mononuclear Complexes with Aza-Capped Hexadentate-N₃S₃ Thiolate Ligands: Crystal Structures of [Ag₃{Co(L)}₂][PF₆]₃ and [Zn₄O{Co(L)}₄][PF₆]₆ (L = N(CH₂NHCH₂CH₂
Tokuda
¹
,
Okamoto
²
,
Konno
³

1999
Inorg. Chem.
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The reaction of an S-bridged Co2(III)Ag3(I) pentanuclear complex, [Ag3[Co(aet)3]2][BF4]3 (aet = NH2CH2CH2S-), with paraformaldehyde in basic acetonitrile, followed by adding aqueous ammonia, produced an aza-capped Co2(III)-Ag3(I) complex, [Ag3[Co(L)]2]3+ ([1]3+) (L = N(CH2NHCH2CH2S-)3). The crystal structure of [1]3+ was determined by X-ray crystallography. [1][PF6]3 x H2O, empirical formula C18H44Ag3Co2F18N8OP3S6, crystallizes in the tetragonal space group 142m with a = 13.012(1) A, c = 24.707(2) A, and Z = 4. In [1]3+ the two aza-capped [Co(L)] units are linked by three Ag(I) atoms, such that the two Co(III) atoms are encapsulated in a macrobicyclic metallocage, [Ag3(I)(L)2]3-. [1]3+ was converted to an aza-capped Co4(III)Zn4(II) octanuclear complex, [Zn4O[Co(L)]4]6+ ([2]6+), by reaction with I- in the presence of Zn2+ and ZnO in water. The crystal structure of [2]6+ was also determined by X-ray crystallography. [2][PF6]6 x 8H2O, empirical formula C36H100Co4F36N16O9P6S12Zn4, crystallizes in the monoclinic space group P2(1/n) with a = 14.33(7) A, b = 25.67(10) A, c = 24.83(6) A, beta = 101.3(3) degrees , and Z = 4. In [2]6+ each of four [Co(L)] units is bound to each trigonal Zn3(II) face of the tetrahedral [Zn4(II)O]6+ core, such that each Co(III) atom is encapsulated in a macrobicyclic [Zn4(II)O(L)] fragment. Treatment of [2]6+ with a basic aqueous solution resulted in a cleavage of the Zn-S bonds to produce an aza-capped Co(III) mononuclear complex, [Co(L)] ([3]), from which [1]3+ is readily reproduced by the reaction with Ag+ in water. All the reactions were found to proceed with retention of the absolute configuration (delta or lambda) of the Co(III) chiral centers; deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and A-[3] were derived from deltadelta-[Ag3[Co(aet)3]2]3+. The contributions to circular dichroism (CD) from the triple helicity in [1]3+, besides from the asymmetric N and S donor atoms and the Co(III) chiral centers in [1]3+ and [2]6+, were estimated by comparing the CD spectra of deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and delta-[3].

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Section: Resultssupporting

confidence: 81%

Section: Resultssupporting

confidence: 73%

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Chiral Properties of Co^III₂Ag^I₃ Pentanuclear, Co^III₄Zn^II₄ Octanuclear, and Co^III Mononuclear Complexes with Aza-Capped Hexadentate-N₃S₃ Thiolate Ligands: Crystal Structures of [Ag₃{Co(L)}₂][PF₆]₃ and [Zn₄O{Co(L)}₄][PF₆]₆ (L = N(CH₂NHCH₂CH₂
Tokuda
¹
,
Okamoto
²
,
Konno
³

1999
Inorg. Chem.
Self Cite
22
0
3
0
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“…1 formed two pairs of racemic isomers, 1a (Δ AA Δ/Λ CC Λ) and 1b (Δ CC Δ/Λ AA Λ), which were separated and optically resolved. To our knowledge, this is the first example of the formation of two pairs of racemic isomers for the S-bridged polynuclear complexes with aet; one racemic and/or one meso isomer have been formed. ,,,− The configurational assignment of the optically active isomers for 1 was successfully made by the CD curve analysis, based on the assumption that the CD contributions from the inner and the outer cobalt chiral centers are additive. This fact indicates that the additivity on CD, which has been recognized mainly for the mononuclear cobalt(III) system, can be applied for the S-bridged polynuclear system with aet or its related sulfur-containing ligand.…”

Section: Discussionmentioning

confidence: 93%

Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co₂(aet)₂}{Co(aet)₃}₂]⁴⁺(aet = 2-Aminoethanethiolate): A Novel S-Bridged Tetranuclear Cobalt(III) Complex Formed by Ligand Transfer from Nickel(II) to Cobalt(III)

1997

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A novel S-bridged tetracobalt(III) complex, [{Co 2 (aet) 2 }{Co(aet) 3 } 2 ] 4+ (1), was prepared by reacting [Ni(aet) 2 ] (aet ) 2-aminoethanethiolate) with [CoCl(NH 3 ) 5 ] 2+ or [CoCl 2 (en) 2 ] + (en ) ethylenediamine) in water. 1 formed two pairs of racemic isomers, 1a and 1b, which were separated by fractional crystallization and/or cation-exchange column chromatography. The crystal structures of 1a and 1b were determined by X-ray crystallography. 1a(NO 3 ) 4 ‚2H 2 O, empirical formula C 16 H 52 N 12 O 14 S 8 Co 4 , crystallizes in the triclinic space group P1 h with a ) 13.585(3) Å, b ) 15.132(3) Å, c ) 10.699(2) Å, R ) 101.46(1)°, β ) 104.78(1)°, γ ) 95.89(1)°, and Z ) 2. 1b(NO 3 ) 4 ‚2H 2 O crystallizes in the monoclinic space group Cc with a ) 26.633(6) Å, b ) 10.204(1) Å, c ) 15.907( 4) Å, β ) 110.33(1)°, and Z ) 4. Each of 1a and 1b contains four cobalt atoms which are linked by one double and two triple sulfur bridges in a boat-type metal array. The two outer cobalt atoms have a fac-Co(N) 3 -(S) 3 chromophore, while the two inner cobalt atoms have a Co(N)(S) 5 chromophore. The isomers possible for 1 are discriminated by a combination of the ∆ or Λ configuration for the outer cobalt centers and the C or A configuration for the inner cobalt centers, and X-ray analyses indicated that 1a and 1b have the ∆AA∆/ΛCCΛ and ∆CC∆/ΛAAΛ configurations, respectively. Each of 1a and 1b was optically resolved, and their electronic absorption, circular dichroism (CD), and NMR spectral properties are also reported. The additivity on CD was considered to assign the absolute configuration for the optically resolved isomers of 1a and 1b.

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

Yamada

Hirano

Fujita

et al. 2005

Inorganica Chimica Acta

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Synthesis and some properties of T-cage type CoIII4HgII4 and RhIII4HgII4 octanuclear complexes with 2-aminoethanethiolate

Cited by 20 publications

References 12 publications

Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co₂(aet)₂}{Co(aet)₃}₂]⁴⁺(aet = 2-Aminoethanethiolate): A Novel S-Bridged Tetranuclear Cobalt(III) Complex Formed by Ligand Transfer from Nickel(II) to Cobalt(III)

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

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Synthesis and some properties of T-cage type CoIII4HgII4 and RhIII4HgII4 octanuclear complexes with 2-aminoethanethiolate

Cited by 20 publications

References 12 publications

Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co2(aet)2}{Co(aet)3}2]4+(aet = 2-Aminoethanethiolate): A Novel S-Bridged Tetranuclear Cobalt(III) Complex Formed by Ligand Transfer from Nickel(II) to Cobalt(III)

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

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Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co₂(aet)₂}{Co(aet)₃}₂]⁴⁺(aet = 2-Aminoethanethiolate): A Novel S-Bridged Tetranuclear Cobalt(III) Complex Formed by Ligand Transfer from Nickel(II) to Cobalt(III)