Trans effects in octahedral complexes:  substitution of chloromethyl- and dichloromethylpentaaquochromium(III) ions by thiocyanate ion

Bushey, William R.; Espenson, James H.

doi:10.1021/ic50177a020

Cited by 7 publications

(1 citation statement)

References 2 publications

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“…Bushey and Esperson proposed[44] a large trans labilizing effect of alkyl groups (-CH 2 Cl or -CHCl 2 ) for the 1:1 substitution of H 2 O with NCSin [Cr(H 2 O) 5 CH 2 Cl] 2+ and [Cr(H 2 O) 5 CHCl 2 ] 2+ . The kinetic data indicate that this reaction proceeds via either an S N 1(dissociative) or an ion-pairing mechanism.…”

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Mechanistic study of the aquation of nutritional supplement chromium chloride and other chromium(III) dihalides

Uddin

Poirier

Henry

2016

Computational and Theoretical Chemistry

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The mechanism for aquation of dihalotetraaquachromium(III) complexes (trans-[Cr(H 2 O) 4 TX] + , where X or T = Cl, Br, or I), including a common component of many nutritional supplements (X, T = Cl) has been investigated using density functional theory. A number of mechanistic pathways were explored including associative interchange (I a), and dissociative (D) mechanisms. The overall activation enthalpy for the D pathway of the dichloro (trans-[Cr (H 2 O) 4 Cl 2 ]) system calculated at the PBE0/cc-pVDZ level, with inclusion of an explicit outer sphere water molecule and in aqueous solution (PCM), is in excellent agreement with the experimental result. The results provide a detailed understanding of the mechanism for the hydrolysis of trans-Cr(III) complexes, which could be useful in understanding the speciation of Cr(III) complexes in physiological environments.

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confidence: 99%

Mechanistic study of the aquation of nutritional supplement chromium chloride and other chromium(III) dihalides

Uddin

Poirier

Henry

2016

Computational and Theoretical Chemistry

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ChemInform Abstract: TRANS EFFECTS IN OCTAHEDRAL COMPLEXES‐ SUBSTITUTION OF CHLOROMETHYL‐ AND DICHLOROMETHYLPENTAAQUOCHROMIUM(III) IONS BY THIOCYANATE ION

Bushey¹,

Espenson²

1978

Chemischer Informationsdienst

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Mechanistic investigation of halopentaaquachromium(III) complexes: Comparison of computational and experimental results

Uddin

Ralph

Henry

2015

Computational and Theoretical Chemistry

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This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Activation enthalpies determined at the PBE0/cc-pVDZ level, in aqueous solution (PCM), are in excellent agreement with the experimental results (MAD is 1.0 kJ mol 1 ). Reaction profiles were analysed in terms of deformation energies and activation volumes to explain the observed trends.

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Trans effects in octahedral complexes: substitution of chloromethyl- and dichloromethylpentaaquochromium(III) ions by thiocyanate ion

Cited by 7 publications

References 2 publications

Mechanistic study of the aquation of nutritional supplement chromium chloride and other chromium(III) dihalides

Mechanistic study of the aquation of nutritional supplement chromium chloride and other chromium(III) dihalides

ChemInform Abstract: TRANS EFFECTS IN OCTAHEDRAL COMPLEXES‐ SUBSTITUTION OF CHLOROMETHYL‐ AND DICHLOROMETHYLPENTAAQUOCHROMIUM(III) IONS BY THIOCYANATE ION

Mechanistic investigation of halopentaaquachromium(III) complexes: Comparison of computational and experimental results

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