NMR and kinetic studies of the interactions of [Au(cis -DACH)Cl2]Cl and [Au(cis -DACH)2]Cl3 with potassium cyanide in aqueous solution

Adam A.A. Seliman; Muhammad Altaf; Abdel Nasser Kawde; Mohammed I.M. Wazeer; Anvarhusein A. Isab

doi:10.1080/00958972.2014.971020

NMR and kinetic studies of the interactions of [Au(cis -DACH)Cl₂]Cl and [Au(cis -DACH)₂]Cl₃ with potassium cyanide in aqueous solution

Adam A.A. Seliman
, Muhammad Altaf
, Abdel Nasser Kawde
, Mohammed I.M. Wazeer
, Anvarhusein A. Isab^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

The interactions of [Au(cis-DACH)Cl₂]Cl and [Au(cis-DACH)₂]Cl₃ [where cis-DACH is cis-1,2-diaminocyclohexane] with enriched KCN were carried out in CD₃OD and D₂O, respectively. The reaction pathways of these complexes were studied by ¹H, ¹³C, ¹⁵N NMR, UV spectrophotometry, and electrochemistry. The kinetic data for the reaction of cyanide with [Au(cis-DACH)₂]Cl₃ are k = 18 M^-1s^-1, H^≠ = 11 kJ M^-1, S^≠ = -185 JK^-1 M^-1, and E_a = 13 kJ M^-1 with square wave voltammetric (SWV) peak +1.35 V, whereas the kinetic data for the reaction of cyanide ion with [Au(cis-DACH)Cl₂]Cl are k = 148 M^-1s^-1, H^≠ = 39 kJM^-1, S^≠ = -80 JK^-1 M^-1, and E_a = 42 kJM^-1 along with SWV peak +0.82 V, indicating much higher reactivity of [Au(cis-DACH)Cl₂]Cl toward cyanide than [Au(cis-DACH)₂]Cl₃. The interaction of these complexes with potassium cyanide resulted in an unstable [Au(¹³CN)₄]^- species which readily underwent reductive elimination reaction to generate [Au(¹³CN)₂]^- and cyanogen.

Original language	English
Pages (from-to)	3431-3443
Number of pages	13
Journal	Journal of Coordination Chemistry
Volume	67
Issue number	21
DOIs	https://doi.org/10.1080/00958972.2014.971020
State	Published - 2 Nov 2014

Bibliographical note

Publisher Copyright:
© 2014 Taylor & Francis.

Keywords

KCN
Rate constant
Reductive elimination
[(cis-DACH)AuCl]Cl complex

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Materials Chemistry

Access to Document

10.1080/00958972.2014.971020

Cite this

@article{5ea0a2d5da6f4078bba065a823e9bf23,

title = "NMR and kinetic studies of the interactions of [Au(cis -DACH)Cl2]Cl and [Au(cis -DACH)2]Cl3 with potassium cyanide in aqueous solution",

abstract = "The interactions of [Au(cis-DACH)Cl2]Cl and [Au(cis-DACH)2]Cl3 [where cis-DACH is cis-1,2-diaminocyclohexane] with enriched KCN were carried out in CD3OD and D2O, respectively. The reaction pathways of these complexes were studied by 1H, 13C, 15N NMR, UV spectrophotometry, and electrochemistry. The kinetic data for the reaction of cyanide with [Au(cis-DACH)2]Cl3 are k = 18 M-1s-1, H≠ = 11 kJ M-1, S≠ = -185 JK-1 M-1, and Ea = 13 kJ M-1 with square wave voltammetric (SWV) peak +1.35 V, whereas the kinetic data for the reaction of cyanide ion with [Au(cis-DACH)Cl2]Cl are k = 148 M-1s-1, H≠ = 39 kJM-1, S≠ = -80 JK-1 M-1, and Ea = 42 kJM-1 along with SWV peak +0.82 V, indicating much higher reactivity of [Au(cis-DACH)Cl2]Cl toward cyanide than [Au(cis-DACH)2]Cl3. The interaction of these complexes with potassium cyanide resulted in an unstable [Au(13CN)4]- species which readily underwent reductive elimination reaction to generate [Au(13CN)2]- and cyanogen.",

keywords = "KCN, Rate constant, Reductive elimination, [(cis-DACH)AuCl]Cl complex",

author = "Seliman, \{Adam A.A.\} and Muhammad Altaf and Kawde, \{Abdel Nasser\} and Wazeer, \{Mohammed I.M.\} and Isab, \{Anvarhusein A.\}",

note = "Publisher Copyright: {\textcopyright} 2014 Taylor \& Francis.",

year = "2014",

month = nov,

day = "2",

doi = "10.1080/00958972.2014.971020",

language = "English",

volume = "67",

pages = "3431--3443",

journal = "Journal of Coordination Chemistry",

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T1 - NMR and kinetic studies of the interactions of [Au(cis -DACH)Cl2]Cl and [Au(cis -DACH)2]Cl3 with potassium cyanide in aqueous solution

AU - Seliman, Adam A.A.

AU - Altaf, Muhammad

AU - Kawde, Abdel Nasser

AU - Wazeer, Mohammed I.M.

AU - Isab, Anvarhusein A.

PY - 2014/11/2

Y1 - 2014/11/2

N2 - The interactions of [Au(cis-DACH)Cl2]Cl and [Au(cis-DACH)2]Cl3 [where cis-DACH is cis-1,2-diaminocyclohexane] with enriched KCN were carried out in CD3OD and D2O, respectively. The reaction pathways of these complexes were studied by 1H, 13C, 15N NMR, UV spectrophotometry, and electrochemistry. The kinetic data for the reaction of cyanide with [Au(cis-DACH)2]Cl3 are k = 18 M-1s-1, H≠ = 11 kJ M-1, S≠ = -185 JK-1 M-1, and Ea = 13 kJ M-1 with square wave voltammetric (SWV) peak +1.35 V, whereas the kinetic data for the reaction of cyanide ion with [Au(cis-DACH)Cl2]Cl are k = 148 M-1s-1, H≠ = 39 kJM-1, S≠ = -80 JK-1 M-1, and Ea = 42 kJM-1 along with SWV peak +0.82 V, indicating much higher reactivity of [Au(cis-DACH)Cl2]Cl toward cyanide than [Au(cis-DACH)2]Cl3. The interaction of these complexes with potassium cyanide resulted in an unstable [Au(13CN)4]- species which readily underwent reductive elimination reaction to generate [Au(13CN)2]- and cyanogen.

AB - The interactions of [Au(cis-DACH)Cl2]Cl and [Au(cis-DACH)2]Cl3 [where cis-DACH is cis-1,2-diaminocyclohexane] with enriched KCN were carried out in CD3OD and D2O, respectively. The reaction pathways of these complexes were studied by 1H, 13C, 15N NMR, UV spectrophotometry, and electrochemistry. The kinetic data for the reaction of cyanide with [Au(cis-DACH)2]Cl3 are k = 18 M-1s-1, H≠ = 11 kJ M-1, S≠ = -185 JK-1 M-1, and Ea = 13 kJ M-1 with square wave voltammetric (SWV) peak +1.35 V, whereas the kinetic data for the reaction of cyanide ion with [Au(cis-DACH)Cl2]Cl are k = 148 M-1s-1, H≠ = 39 kJM-1, S≠ = -80 JK-1 M-1, and Ea = 42 kJM-1 along with SWV peak +0.82 V, indicating much higher reactivity of [Au(cis-DACH)Cl2]Cl toward cyanide than [Au(cis-DACH)2]Cl3. The interaction of these complexes with potassium cyanide resulted in an unstable [Au(13CN)4]- species which readily underwent reductive elimination reaction to generate [Au(13CN)2]- and cyanogen.

KW - KCN

KW - Rate constant

KW - Reductive elimination

KW - [(cis-DACH)AuCl]Cl complex

UR - https://www.scopus.com/pages/publications/84943603091

U2 - 10.1080/00958972.2014.971020

DO - 10.1080/00958972.2014.971020

M3 - Article

AN - SCOPUS:84943603091

SN - 0095-8972

VL - 67

SP - 3431

EP - 3443

JO - Journal of Coordination Chemistry

JF - Journal of Coordination Chemistry

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