DOI: 10.1246/bcsj.49.1027. Derivatographic Studies on Transition Metal Complexes. XVII. Solid-phase Deaquation-anation of Some Optically Active Aqua

Derivatographic Studies on Transition Metal Complexes. XVII. Solid-phase Deaquation-anation of Some Optically Active Aqua—cobalt(III) Complexes

10.1246/bcsj.49.1027

Crossref journal-article

Oxford University Press (OUP)

Bulletin of the Chemical Society of Japan (286)

Abstract

Abstract Stereochemical changes involved in the solid-phase deaquation-anation of the following optically active aqua-cobalt(III) complexes were investigated: (+)546-cis-[Co(H2O)2en2]X3·2H2O (X=Cl or Br), (+)589-cis-α[CoCl(H2O)en2]Cla·H2O, (−)589-cis-[CoCl(H2O)en2]Br2·H2O, (+)589-α-[CoCl(H2O)trien]Cl2·H2O and (+)589-α-[CoCl(H2O)trien]Br2·2H2O, where en and trien denote ethylenediamine and triethylenetetramine, respectively. Thermal deaquation-anation processes for each complex were observed with a derivatograph, polarimeter, and UV and CD spectrophotometers. cis-[Co(H2O)2en2]Cl3·2H2O was converted into cis-[CoCl(H2O)en2]Cl2 at first and then cis-[CoCl2en2]Cl; the stereochemical changes during the first step and the second step were found to be retention and racemization, respectively. In contrast, a predominant stereochemical change involved in the deaquation-anation of cis-[Co(H20)2en2]Br3·2H2O was cis-to-trans isomerization. The deaquation-anation of cis-[CoCl(H2O)en2]Cl2·H2O and cis-[CoCl(H2O)en2]Br2·2H2O was found to be accompanied by racemization and by greater parts of cis-to-trans isomerization, respectively. However, both α-[CoCl(H2O)trien]Cl2·H2O and α-[CoCl(H2O)trien]Br2·2H2O undergo deaquation-anation with retention.

Bibliography

Tsughiya, R., Omote, M., Uehara, A., & Kyuno, E. (1976). Derivatographic Studies on Transition Metal Complexes. XVII. Solid-phase Deaquation-anation of Some Optically Active Aquaâcobalt(III) Complexes. Bulletin of the Chemical Society of Japan, 49(4), 1027â1031.

Authors 4

Ryokichi Tsughiya (first)
Masakatsu Omote (additional)
Akira Uehara (additional)
Eishin Kyuno (additional)

References 16 Referenced 4

10.1246/bcsj.48.2805
10.1016/0040-6031(75)85070-2
{'key': '2024011704023878800_r3'}
{'key': '2024011704023878800_r4'}
10.1016/0022-1902(70)80551-6
10.1016/0040-6031(70)85021-3
{'key': '2024011704023878800_r7'}
10.1021/ja00892a001
{'key': '2024011704023878800_r9'}
10.1021/ja00948a009
{'key': '2024011704023878800_r11'}
10.1002/9780470132401.ch44
10.1016/0040-6031(75)85022-2
10.1021/ja01072a013
10.1021/ja01009a600
10.1021/ja00958a006

Dates

Type	When
Created	19 years, 1 month ago (July 19, 2006, 10:45 p.m.)
Deposited	1 year, 7 months ago (Jan. 16, 2024, 11:02 p.m.)
Indexed	1 year, 7 months ago (Jan. 18, 2024, 5:53 a.m.)
Issued	49 years, 5 months ago (April 1, 1976)
Published	49 years, 5 months ago (April 1, 1976)
Published Online	19 years, 4 months ago (April 19, 2006)
Published Print	49 years, 5 months ago (April 1, 1976)

Funders 0

None

BibTeX

@article{Tsughiya_1976, title={Derivatographic Studies on Transition Metal Complexes. XVII. Solid-phase Deaquation-anation of Some Optically Active Aqua—cobalt(III) Complexes}, volume={49}, ISSN={1348-0634}, url={http://dx.doi.org/10.1246/bcsj.49.1027}, DOI={10.1246/bcsj.49.1027}, number={4}, journal={Bulletin of the Chemical Society of Japan}, publisher={Oxford University Press (OUP)}, author={Tsughiya, Ryokichi and Omote, Masakatsu and Uehara, Akira and Kyuno, Eishin}, year={1976}, month=apr, pages={1027–1031} }

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  "abstract": "<jats:title>Abstract</jats:title>\n               <jats:p>Stereochemical changes involved in the solid-phase deaquation-anation of the following optically active aqua-cobalt(III) complexes were investigated: (+)546-cis-[Co(H2O)2en2]X3\u00b72H2O (X=Cl or Br), (+)589-cis-\u03b1[CoCl(H2O)en2]Cla\u00b7H2O, (\u2212)589-cis-[CoCl(H2O)en2]Br2\u00b7H2O, (+)589-\u03b1-[CoCl(H2O)trien]Cl2\u00b7H2O and (+)589-\u03b1-[CoCl(H2O)trien]Br2\u00b72H2O, where en and trien denote ethylenediamine and triethylenetetramine, respectively. Thermal deaquation-anation processes for each complex were observed with a derivatograph, polarimeter, and UV and CD spectrophotometers. cis-[Co(H2O)2en2]Cl3\u00b72H2O was converted into cis-[CoCl(H2O)en2]Cl2 at first and then cis-[CoCl2en2]Cl; the stereochemical changes during the first step and the second step were found to be retention and racemization, respectively. In contrast, a predominant stereochemical change involved in the deaquation-anation of cis-[Co(H20)2en2]Br3\u00b72H2O was cis-to-trans isomerization. The deaquation-anation of cis-[CoCl(H2O)en2]Cl2\u00b7H2O and cis-[CoCl(H2O)en2]Br2\u00b72H2O was found to be accompanied by racemization and by greater parts of cis-to-trans isomerization, respectively. However, both \u03b1-[CoCl(H2O)trien]Cl2\u00b7H2O and \u03b1-[CoCl(H2O)trien]Br2\u00b72H2O undergo deaquation-anation with retention.</jats:p>",
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