Subtle ligand/media effects. Modulation of cis/trans isomerism in hydrogen peroxide oxidation of Pt(II) to Pt(IV) complexes

Young A. Lee; Kyung Ho Yoo; Ok Sang Jung

doi:10.1246/bcsj.76.107

Subtle ligand/media effects. Modulation of cis/trans isomerism in hydrogen peroxide oxidation of Pt(II) to Pt(IV) complexes

Young A. Lee^*
, Kyung Ho Yoo
, Ok Sang Jung

^*Corresponding author for this work

Department of Chemistry

Korea Institute of Science and Technology

Research output: Contribution to journal › Journal article › peer-review

14 Scopus citations

Abstract

The modulation of cis/trans isomerism on the oxidation of Pt^II to Pt^IV via subtle ligand/media effects has been established. The reaction of [Pt^II(O-O)(dpda)] (O-O = 1,1-cyclobutanedicarboxylate (cbdc), dibenzylmalonate (dbm); dpda = 2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in acetic acid produces cis-[Pt^IV(O₂CCH₃)₂(O-O)(dpda)], while the reaction in acetic anhydride gives trans-[Pt^IV(O₂CCH₃)₂(O-O)(dpda)]. The crystal structures of cis- [Pt^IV(O₂CCH₃)₂(cbdc)(dpda)] (orthorhombic Pbca, a = 11.148(2) Å, b = 14.188(5) Å, c = 23.425(3) Å, V = 3705(2) Å³, Z = 8, R = 0.0525) and trans-[Pt^IV(O₂CCH₃)₂ (cbdc)(dpda)]·3H₂O (monoclinic P2₁/c, a = 11.479(2) Å, b = 13.426(3) Å, c = 14.640(5) Å, β = 108.73(2)°, V = 2136.8(9) Å³, Z = 4, R = 0.0251) have been solved and refined. The AcO-Pt-AcO angle (87.4(5)°) of the cis isomer presents a striking contrast to that (172.5(1)°) of the trans isomer. The trans isomer is retained in aqueous solution, but the cis isomer is very slowly converted to the trans isomer in both water and acetic acid.

Original language	English
Pages (from-to)	107-110
Number of pages	4
Journal	Bulletin of the Chemical Society of Japan
Volume	76
Issue number	1
DOIs	https://doi.org/10.1246/bcsj.76.107
State	Published - 2003

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@article{e986c078064043beb342e6465e649fe4,

title = "Subtle ligand/media effects. Modulation of cis/trans isomerism in hydrogen peroxide oxidation of Pt(II) to Pt(IV) complexes",

abstract = "The modulation of cis/trans isomerism on the oxidation of PtII to PtIV via subtle ligand/media effects has been established. The reaction of [PtII(O-O)(dpda)] (O-O = 1,1-cyclobutanedicarboxylate (cbdc), dibenzylmalonate (dbm); dpda = 2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in acetic acid produces cis-[PtIV(O2CCH3)2(O-O)(dpda)], while the reaction in acetic anhydride gives trans-[PtIV(O2CCH3)2(O-O)(dpda)]. The crystal structures of cis- [PtIV(O2CCH3)2(cbdc)(dpda)] (orthorhombic Pbca, a = 11.148(2) {\AA}, b = 14.188(5) {\AA}, c = 23.425(3) {\AA}, V = 3705(2) {\AA}3, Z = 8, R = 0.0525) and trans-[PtIV(O2CCH3)2 (cbdc)(dpda)]·3H2O (monoclinic P21/c, a = 11.479(2) {\AA}, b = 13.426(3) {\AA}, c = 14.640(5) {\AA}, β = 108.73(2)°, V = 2136.8(9) {\AA}3, Z = 4, R = 0.0251) have been solved and refined. The AcO-Pt-AcO angle (87.4(5)°) of the cis isomer presents a striking contrast to that (172.5(1)°) of the trans isomer. The trans isomer is retained in aqueous solution, but the cis isomer is very slowly converted to the trans isomer in both water and acetic acid.",

author = "Lee, \{Young A.\} and Yoo, \{Kyung Ho\} and Jung, \{Ok Sang\}",

year = "2003",

doi = "10.1246/bcsj.76.107",

language = "English",

volume = "76",

pages = "107--110",

journal = "Bulletin of the Chemical Society of Japan",

issn = "0009-2673",

number = "1",

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TY - JOUR

T1 - Subtle ligand/media effects. Modulation of cis/trans isomerism in hydrogen peroxide oxidation of Pt(II) to Pt(IV) complexes

AU - Lee, Young A.

AU - Yoo, Kyung Ho

AU - Jung, Ok Sang

PY - 2003

Y1 - 2003

N2 - The modulation of cis/trans isomerism on the oxidation of PtII to PtIV via subtle ligand/media effects has been established. The reaction of [PtII(O-O)(dpda)] (O-O = 1,1-cyclobutanedicarboxylate (cbdc), dibenzylmalonate (dbm); dpda = 2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in acetic acid produces cis-[PtIV(O2CCH3)2(O-O)(dpda)], while the reaction in acetic anhydride gives trans-[PtIV(O2CCH3)2(O-O)(dpda)]. The crystal structures of cis- [PtIV(O2CCH3)2(cbdc)(dpda)] (orthorhombic Pbca, a = 11.148(2) Å, b = 14.188(5) Å, c = 23.425(3) Å, V = 3705(2) Å3, Z = 8, R = 0.0525) and trans-[PtIV(O2CCH3)2 (cbdc)(dpda)]·3H2O (monoclinic P21/c, a = 11.479(2) Å, b = 13.426(3) Å, c = 14.640(5) Å, β = 108.73(2)°, V = 2136.8(9) Å3, Z = 4, R = 0.0251) have been solved and refined. The AcO-Pt-AcO angle (87.4(5)°) of the cis isomer presents a striking contrast to that (172.5(1)°) of the trans isomer. The trans isomer is retained in aqueous solution, but the cis isomer is very slowly converted to the trans isomer in both water and acetic acid.

AB - The modulation of cis/trans isomerism on the oxidation of PtII to PtIV via subtle ligand/media effects has been established. The reaction of [PtII(O-O)(dpda)] (O-O = 1,1-cyclobutanedicarboxylate (cbdc), dibenzylmalonate (dbm); dpda = 2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in acetic acid produces cis-[PtIV(O2CCH3)2(O-O)(dpda)], while the reaction in acetic anhydride gives trans-[PtIV(O2CCH3)2(O-O)(dpda)]. The crystal structures of cis- [PtIV(O2CCH3)2(cbdc)(dpda)] (orthorhombic Pbca, a = 11.148(2) Å, b = 14.188(5) Å, c = 23.425(3) Å, V = 3705(2) Å3, Z = 8, R = 0.0525) and trans-[PtIV(O2CCH3)2 (cbdc)(dpda)]·3H2O (monoclinic P21/c, a = 11.479(2) Å, b = 13.426(3) Å, c = 14.640(5) Å, β = 108.73(2)°, V = 2136.8(9) Å3, Z = 4, R = 0.0251) have been solved and refined. The AcO-Pt-AcO angle (87.4(5)°) of the cis isomer presents a striking contrast to that (172.5(1)°) of the trans isomer. The trans isomer is retained in aqueous solution, but the cis isomer is very slowly converted to the trans isomer in both water and acetic acid.

UR - https://www.scopus.com/pages/publications/0037253324

U2 - 10.1246/bcsj.76.107

DO - 10.1246/bcsj.76.107

M3 - Journal article

AN - SCOPUS:0037253324

SN - 0009-2673

VL - 76

SP - 107

EP - 110

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

IS - 1

ER -

Subtle ligand/media effects. Modulation of cis/trans isomerism in hydrogen peroxide oxidation of Pt(II) to Pt(IV) complexes

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