Translational diffusion of transition metal complexes

Kowert, Bruce A.; Hughes, Angela M.; Dang, Nhan C.; Martin, Michael; Cheung, Gia H; Tran, Hung D.; Reed, Joshua P.

doi:10.1016/s0301-0104(99)00231-1

Cited by 7 publications

(14 citation statements)

References 37 publications

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“…The r t values for [Ni(mnt) 2 ] − are essentially the same in acetonitrile (ACN), EtOH, acetone, and BuOH (≈3.60 Å) and are smaller than those for [Ni(mnt) 2 ] 2− in EtOH, acetone, and ACN (≈4.50 Å). 16,31 These results are in agreement with electrochemical, 32 conductivity, 33,34 and vapor phase osmometry 32 data in ACN that showed [Ni(mnt) 2 ] 2− but not [Ni(mnt) 2 ] − was ion-paired with Et 4 N + (we used Bu 4 N + ). The absence of ion pairing between [Ni(mnt) 2 ] − and Bu 4 N + in diglyme is consistent with infrared studies that indicated a lack of association between Bu 4 N + and CF 3 SO 3 − in both diglyme 35 and triglyme 36 (triethylene glycol dimethyl ether).…”

Section: Discussionsupporting

confidence: 89%

“… a From Table 1 of ref 31 except for diglyme from Firman, M.; Xu, M.; Eyring, E. M.; Petrucci, S. J. Phys. Chem .…”

Section: Figurementioning

confidence: 99%

“…Chem . 1993 , 97, 3606–3613. b The entries are the averages of the values given in Table 2 of ref 31; typical uncertainties are ±0.20 Å. c The entries are from Table 1 from ref 18. …”

Section: Figurementioning

confidence: 99%

“… b The entries are the averages of the values given in Table 2 of ref 31; typical uncertainties are ±0.20 Å. …”

Section: Figurementioning

confidence: 99%

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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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Section: Discussionsupporting

confidence: 89%

“… a From Table 1 of ref 31 except for diglyme from Firman, M.; Xu, M.; Eyring, E. M.; Petrucci, S. J. Phys. Chem .…”

Section: Figurementioning

confidence: 99%

“…Chem . 1993 , 97, 3606–3613. b The entries are the averages of the values given in Table 2 of ref 31; typical uncertainties are ±0.20 Å. c The entries are from Table 1 from ref 18. …”

Section: Figurementioning

confidence: 99%

“… b The entries are the averages of the values given in Table 2 of ref 31; typical uncertainties are ±0.20 Å. …”

Section: Figurementioning

confidence: 99%

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

Kowert

Stemmler

et al. 2012

J. Phys. Chem. B

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“…Table 3 also presents the center‐of‐mass diffusion coefficient of the non‐macromolecules ( D A with A = 1, …, 6) in the reaction mixture at a T pol of 298 K and for an equal mass fraction of monomer, solvent, and polymer (i.e., w 1 / w 6 / w 7 = 1:1:1). The calculated center‐of‐mass diffusion coefficient of MMA ( A = 1) has the same order of magnitude as the experimental data reported by Griffiths et al69 The calculated center‐of‐mass diffusion coefficients of both the transition metal complexes ( A = 4 and 5) have the same order of magnitude as center‐of‐mass diffusion coefficients of transition metal complexes measured by Kowert et al70 Note that the center‐of‐mass diffusion coefficients of the transition metal complexes are significantly lower than the center‐of‐mass diffusion coefficient of MMA, which is mainly due to their larger molar critical free volume for a diffusional jump (i.e., $V_A^{\rm *}$ M j , A ) as compared to MMA.…”

Section: Kinetic Modelsupporting

confidence: 83%

Methodology for Kinetic Modeling of Atom Transfer Radical Polymerization

D’hooge

Reyniers

Marin

2009

Macro Reaction Engineering

134

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A methodology for kinetic modeling of atom transfer radical polymerization is developed allowing to calculate the monomer conversion, the fraction of polymer molecules having end group functionality, the full molar mass distribution (MMD) of the dormant polymer and the number, mass, and z based average molar mass of the dead and dormant polymer. The developed methodology is based on an extension of the method of moments and allows an accurate description of the contribution of the polymer molecules with a high molar mass to the MMD of the polymer. Diffusional limitations on all considered reaction steps are systematically accounted for. Simulation results are in good agreement with experimental observations. Moreover, the methodology allows a detailed description of the broadness and the skewness of the MMD of the polymer.

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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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Translational diffusion of transition metal complexes

Cited by 7 publications

References 37 publications

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

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

Methodology for Kinetic Modeling of Atom Transfer Radical Polymerization

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

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