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Kinetics and mechanism of reaction of trans-(diaqua)(N,N′-ethylene-bis-salicylidenimine) chromium(iii) with sulfur(iv): The labilizing effect of coordinated sulfite by Anadi C. Dash; Achyuta N. Acharya; Prakash Mohanty; Arabinda Das is a Chemistry article available to read on EtoBox.

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The reaction of trans-[Cr(Salen)(OH 2 ) 2 ] ϩ with aqueous sulfite yields trans-[Cr(Salen)(OH 2 )(OSO 2 9 O)] Ϫ (O-bonded isomer). The rate and activation parameter data for the formation of the sulfito complex are consistent with a mechanism involving rate-limiting addition of SO 2 to the bond. The complex ions, trans-[(OH 2 )Cr(Salen)(OSO 2 9O)] Ϫ , III Cr 9OH and trans-undergo reversible anation by NCS Ϫ , imidazole, 2Ϫ Ϫ [(OH)Cr(Salen)(OSO 9O)] , N , 2 3 and pyridine resulting in the formation of trans-( for (nϩ1)Ϫ [XCr(Salen)(OSO 9O)] n ϭ 1 Xϭ 2 NCS Ϫ , and 0 for and pyridine) predominantly via dissociative interchange Ϫ N , X ϭ imidazole 3 mechanism. The labilizing action of the coordinated sulfite on the trans-bond in III Cr -X follows the sequence: ca. ca. imidazole. (nϩ1)Ϫ Ϫ Ϫ trans-[XCr(Salen)(OSO )] NCS Ͻ pyridine N 2 3 Data analysis indicated that the coordinated sulfite has little trans activating influence.

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Author

Anadi C. Dash; Achyuta N. Acharya; Prakash Mohanty; Arabinda Das

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); John Wiley & Sons Inc.; Wiley (ISSN 0538-8066)

Published

1998

Language

EN

Field

Chemistry (Physical Sciences)