Diglyme adduct of dipotassium bis(<i>tert</i>-butyl[8]annulene)ytterbate(II)

Kinsley, Steven A.; Streitwieser, A.; Zalkin, A.

doi:10.1107/s0108270186093332

Cited by 8 publications

(11 citation statements)

References 1 publication

(2 reference statements)

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“…The similarity in these two groups is ascribed to a common electronic feature; they are characterized as a highly ionic complex that depends not on the metal elements, but on the oxidation state. It is reasonable to assume that Ce, Nd, and Ho all take the oxidation state of +3, while both Eu and Yb take that of +2, by analogy to the reported lanthanide complexes. ,− …”

Section: Resultsmentioning

confidence: 98%

“…In the condensed phase, therefore, the alkali metal salts of M alkali + [Ln 3+ (C 8 H 8 2- ) 2 ] are generally prepared, where positively charged M alkali + compensates the discrepancy between 3+ oxidation states of Ln atoms and the negative charge of 4− from two C 8 H 8 ligands. Among 14 lanthanide elements, there are 2+ oxidation state complexes of Eu and Yb that form in bulk as (M alkali + ) 2 [Ln 2+ (C 8 H 8 2- ) 2 ]. − …”

Section: Introductionmentioning

confidence: 99%

“…Among 14 lanthanide elements, there are 2+ oxidation state complexes of Eu and Yb that form in bulk as (M alkali + ) 2 [Ln 2+ (C 8 H 8 2-) 2 ]. [15][16][17] These properties of Ln metals indeed retard studies on neutral and multicore complexes of Ln n (C 8 H 8 ) m . Until now, only two synthetic studies on Ce 2 (C 8 H 8 ) 3 18 and [(C 8 H 8 )Nd(THF) 2 ][(C 8 H 8 ) 2 -Nd] 19 have been reported.…”

Section: Introductionmentioning

confidence: 99%

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Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Ln_n(C₈H₈)_m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

et al. 1998

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Organometallic lanthanide complexes of Ln n (C8H8) m (Ln = lanthanide metals of Ce, Nd, Eu, Ho, and Yb; C8H8 = 1,3,5,7-cyclooctatetraene) were produced by a combination of laser vaporization and molecular beam methods. The complexes having (n, m) = (n, n + 1) for n = 1−5 were prominently produced as magic numbers in the mass spectra. Using mass spectrometry, photoionization spectroscopy, and photoelectron spectroscopy, it is concluded that these magic-numbered complexes form multiple decker sandwich structures in which Ln atoms and C8H8 molecules are alternately piled up. The obtained spectroscopic data show that these sandwich complexes are formed through ionic bonds and are charge transfer complexes, where the Ln atoms are multiply charged cations of Ln k + (k = 2 and 3) and C8H8 molecules are multiply charged anions.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Ln_n(C₈H₈)_m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

et al. 1998

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“…The glymes are well-known cation solvating media 37 and the K + ions also may be coordinated by diglyme. For example, the bis(cyclooctatetraenyl)cerium anion, [Ce(C 8 H 8 ) 2 ] − , and a diglyme-coordinated potassium cation 38 form a contact ion pair and the bis( tert -butyl[8]annulene)ytterbate(II) dianion, [Yb(C 12 H 16 ) 2 ] 2−,39 and 1,3,5,7-tetramethylcyclooctatetraenide, [C 8 H 4 (CH 3 ) 4 ] 2−,40 both form trimers with two potassium-diglyme units.…”

Section: Discussionmentioning

confidence: 99%

Molecular Motion of the Bis(maleonitriledithiolato)nickel Trianion in Solution

Kowert

Stemmler

et al. 2012

J. Phys. Chem. B

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Electron spin resonance (ESR) has been used to study the reorientational motion of the bis(maleonitriledithiolato)nickel trianion, [Ni(mnt)2]3−, in diethylene glycol dimethyl ether (diglyme). [Ni(mnt)2]3− has one unpaired electron and was prepared by reducing the dianion, [Ni(mnt)2]2−, with potassium metal. The trianion and dianion are members of the redox series [Ni(mnt)2]n− with n = 0, 1, 2, 3. The monoanion, [Ni(mnt)2]−, also has S = ½ and its rotational diffusion in diglyme was the subject of previous ESR studies. This made possible the comparison of the reorientational data for two different oxidation states of the same planar complex in the same solvent. Differences were found; isotropic rotational diffusion produced agreement between the trianion’s experimental and calculated spectra while the monoanion’s simulations required axially symmetric reorientation with diffusion about the long in-plane axis three times faster than that about the two perpendicular axes. At a given temperature, the monoanion’s reorientation rates about the long in-plane axis and two perpendicular axes were faster than the trianion’s isotropic rate by factors of ~27 and ~9, respectively. These differences suggest that [Ni(mnt)2]− and [Ni(mnt)2]3− have different shapes and sizes in solution; the monoanion is approximately a prolate ellipsoid while the trianion is larger and more spherical. [Ni(mnt)2]3− appears to be ion-paired while, in accord with results from other techniques, [Ni(mnt)2]− is not.

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“…We assumed the complex ion was planar and used the dianion as a model structure. The cations in both structures were placed above and below the Ni atom using cation‐anion distances from the literature . One structure had the cation‐coordinating diglymes parallel to the complex's long in‐plane axis; both diglymes were perpendicular to the long axis in the other.…”

Section: Resultsmentioning

confidence: 99%

d‐electron count, ion‐pairing and diagonal twist angles in metallo‐bis(dithiolene) complexes

2016

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Electronic structure calculations for late transition metals coordinated by two dithiolene ligands are found to be consistent with existing structures and also predict the geometries of Ni(I) species for which no solid state structures have been reported. Of particular interest are the compounds [M(mnt) ] (M = Ni, Pd, and Pt with n = 1, 2, 3; M = Cu with n = 2). Calculations have been performed with and without ion-paring with M(diglyme) (M = Li, Na, K) and R N (R = Me, Bu). The diagonal twist angle between two NiS planes is found to depend on (i) the metal's d-electron count, spanning from 0° (planar d and d ), to 42° (d ), to 90° (pseudo-tetrahedral d ), and (ii) the identity of the ion-paired cations. Calculated ion-pairing energies are functions of the cation size and charge-density, being larger for alkali-metal coordinated diglyme and smaller for tetra-alkyl ammonium cations. © 2016 Wiley Periodicals, Inc.

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Diglyme adduct of dipotassium bis(tert-butyl[8]annulene)ytterbate(II)

Cited by 8 publications

References 1 publication

Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Ln_n(C₈H₈)_m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Ln_n(C₈H₈)_m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

Molecular Motion of the Bis(maleonitriledithiolato)nickel Trianion in Solution

d‐electron count, ion‐pairing and diagonal twist angles in metallo‐bis(dithiolene) complexes

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Diglyme adduct of dipotassium bis(tert-butyl[8]annulene)ytterbate(II)

Cited by 8 publications

References 1 publication

Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Lnn(C8H8)m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Lnn(C8H8)m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

Molecular Motion of the Bis(maleonitriledithiolato)nickel Trianion in Solution

d‐electron count, ion‐pairing and diagonal twist angles in metallo‐bis(dithiolene) complexes

Contact Info

Product

Resources

About

Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Ln_n(C₈H₈)_m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure

Multiple-Decker Sandwich Complexes of Lanthanide−1,3,5,7-Cyclooctatetraene [Ln_n(C₈H₈)_m] (Ln = Ce, Nd, Eu, Ho, and Yb); Localized Ionic Bonding Structure