Structure and absolute configuration of the (-)D isomer of lithium ethylenediamine-N,N'-diacetato-N,N'-di-3-propionatochromate(III) pentahydrate, (-)D-Li[Cr(EDDDA)].5H2O

HELM, F. T.; Watson, William H.; Radanović, Dušan J.; Douglas, Bodie E.

doi:10.1021/ic50175a040

Cited by 50 publications

(15 citation statements)

References 12 publications

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“…The angle C(4)-N(2)-C( 7) is bisected by the N( 1 )-Cr-N(2) plane. The torsion angles N( l)-Cr-N(2)-C(4) and N(l)-Cr-N(2)-C (7) are almost equal for both the ( S )pdtrp and the (SS)-cydtrp complexes. The chelate conformations at the G' and R ring are almost enantiomeric, especially around the Cr-N-C-C moieties, but with considerable discrepancy around the carboxyl groups as seen from the torsion angles in Table 6.…”

Section: Resultsmentioning

confidence: 95%

Novel diastereoisomers of ethylenediaminetetrapropionato-chromate(III) Part 2. X-Ray structures of diaminetripropionato complexes

Sakagami¹,

Kaizaki²

1992

J. Chem. Soc., Dalton Trans.

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The crystal structures of the complexes [Cr{(S)-pdtrp}(H,O)] 1 [(S)-pdtrp = (S)-propane-1,2diamine-N,N,N'-tripropionate] and [Cr{(SS)-cydtrp}(H,O)] 2 [(SS)-cydtrp = (1 S,2S)-transcyclohexane-l,2-diamine-N,N,N'-tripropionate] were determined by X-ray diffraction methods: 1, monoclinic, space group P2, a = 13.474(9), b = 9.867(3), c = 14.506(5) A, p = 105.85(3)' and Z = 4; 2, triclinic, space group P1, a = 13.938(7), b = 14.01 6(6), c = 13.901 (4) p\, 0: = 106.24(3), p = 11 2.50(3), y =73.21(4)" and Z = 4. The t w o complexes have the same geometrical structure, transequatorial, where t w o propionato chelates attached t o the tertiary amine are co-ordinated meridionally. This structure substantiates that the anomalous C-N bond rupture observed in the t w o of the three diastereoisomers of [Cr(edtp)] -(edtp = ethylenediamine-N,N,N',N'-tetrapropionate) type complexes occurs at the R (relaxed) out-of-plane ring, not at the G (girdling) in-plane ring.

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Section: Resultsmentioning

confidence: 95%

Novel diastereoisomers of ethylenediaminetetrapropionato-chromate(III) Part 2. X-Ray structures of diaminetripropionato complexes

Sakagami¹,

Kaizaki²

1992

J. Chem. Soc., Dalton Trans.

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“…Complexes with hexadentate amino carboxylate ligands exhibit the cis -N 2 O 4 (B) environment if the ligand framework provides sufficient strain relief for binding of the in-plane carboxylates. Examples are found in the structures of Na[Cr(1,3-PDTA)]·H 2 O and Li[Cr(EDDDA)]·5H 2 O …”

Section: Resultsmentioning

confidence: 99%

Ligand Structural Effects on the Electrochemistry of Chromium(III) Amino Carboxylate Complexes

1996

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The aqueous electrochemical behavior of 10 Cr(III) complexes with potentially tri- and hexadentate amino carboxylate ligands is reported and is shown to depend on the composition and spatial arrangement of the donor atom set. Complexes with two amine and four carboxylate donors (N(2)O(4)) and two amine, one aquo, and three carboxylate donors (N(2)O(3)O') in which the N atoms are coordinated cis to one another undergo chemically and electrochemically reversible reduction at ca. -1.4 and ca. -1.2 V vs SCE, respectively. However, complexes with a trans-N(2)O(4) donor atom set, as exemplified by Cr(MIDA)(2)(-) (MIDA(2)(-) = N-methyliminodiacetate), undergo quasi-reversible Cr(III/II) reduction at ca. -1.4 V that is followed by a sequence of reactions which establishes an electrochemical square scheme. The chemical reactions in the scheme involve displacement of a bound carboxylate group following reduction to Cr(II) and its reattachment after reoxidation to Cr(III). This mechanistic sequence is analyzed by digital simulation, and values of formal potentials, transfer coefficients, and chemical and electrochemical rate constants are reported for Cr(MIDA)(2)(-) and its N-ethyl homolog. The difference in electrochemical behavior between cis- and trans-N(2)O(4) complexes is attributed to differences in the Jahn-Teller distortions experienced by these structures upon reduction to Cr(II). It is proposed that simultaneous N-Cr-N bond elongation, which is possible only for trans species, leads to greater strain in the facially coordinated N-alkyliminodiacetate ligand and thus increases the barrier to electron transfer and facilitates Cr-carboxylate bond cleavage after reduction.

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“…With respect to the carboxylate donors, the three possible isomers are shown in Figure 1, where the nomenclature trans(O 5 ) and trans(O 6 ) refers to axial acetato and propionate groups, respectively. 9,10 The sixmembered carboxylate rings of ethylenediamine-N,N′-diacetato-N,N′-dipropionato ion ([eddadp] 4− ) serve better for the formation of less-strained G rings favoring the trans(O 5 ) isomer of [M(eddadp)] n− complexes when M = Co III , 23,24 Cr III , 25,26 and Rh III or Ni II . 11,27,28 It is worth noting that, for Co III and Rh III , the less stable trans(O 5 O 6 ) isomer is also found and characterized.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthetic, Crystallographic, and Computational Study of Copper(II) Complexes of Ethylenediaminetetracarboxylate Ligands

et al. 2013

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Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and H(4)eddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H(4)eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3-propionic acid) have been prepared. An octahedral trans(O(6)) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8H(2)O compound, while Ba[Cu(eddadp)]·8H(2)O is proposed to adopt a trans(O(5)) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial β-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.

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Structure and absolute configuration of the (-)D isomer of lithium ethylenediamine-N,N'-diacetato-N,N'-di-3-propionatochromate(III) pentahydrate, (-)D-Li[Cr(EDDDA)].5H2O

Cited by 50 publications

References 12 publications

Novel diastereoisomers of ethylenediaminetetrapropionato-chromate(III) Part 2. X-Ray structures of diaminetripropionato complexes

Novel diastereoisomers of ethylenediaminetetrapropionato-chromate(III) Part 2. X-Ray structures of diaminetripropionato complexes

Ligand Structural Effects on the Electrochemistry of Chromium(III) Amino Carboxylate Complexes

Synthetic, Crystallographic, and Computational Study of Copper(II) Complexes of Ethylenediaminetetracarboxylate Ligands

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