Copper(II) complexes of hydrolysis products of the anticancer bis(3,5-dioxopiperazin-1-yl)alkanes. Displacement of co-ordinated carboxylate ligands by deprotonated amide groups in basic solution

N N DAEID, K B NOLAN, L P RYAN

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Abstract

The copper(II) complexes of the diacid diamide -O2CCH2(H2NOCCH2)NCH2CHRN(CH2CONH2)CH2CO2- (R = H, L3; Me, L4) which have in-plane 2N(amine,) 2 O(carboxylate) ligands at pH 6 undergo amide group deprotonation in basic solution to give CuN(amine)2N- (amide)2 chromophores resulting from the displacement of the in-plane carboxylate ligands by the superior sigma-donating, deprotonated, amide nitrogens. The concentration pK(a) values for the deprotonations at 25-degrees-C, l = 0.1 mol dm-3 are 9.19 +/- 0.02 and 9.87 +/- 0.02 for [CuL3], and 8.60 +/- 0.02 and 9.81 +/- 0.02 for [CuL4]. The unexpectedly large differences in the first pK(a) values is attributed to a steric interaction between the methyl substituent and an axially co-ordinated CH2CONH2 group, in the complex of L4 which is relieved as a result of the first ionisation step.

LanguageEnglish
Pages2301-2304
Number of pages4
JournalJournal of the Chemical Society, Dalton Transactions
Issue number9
DOIs
Publication statusPublished - Sep 1991

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Alkanes
Amides
Copper
Hydrolysis
Deprotonation
Ligands
Amines
Diamide
Chromophores
Ionization
Nitrogen

Keywords

  • peptides
  • agents
  • hydrolysis products
  • anticancer agent

Cite this

@article{3d76623f33354a2fadbcff36ee7d2fe9,
title = "Copper(II) complexes of hydrolysis products of the anticancer bis(3,5-dioxopiperazin-1-yl)alkanes. Displacement of co-ordinated carboxylate ligands by deprotonated amide groups in basic solution",
abstract = "The copper(II) complexes of the diacid diamide -O2CCH2(H2NOCCH2)NCH2CHRN(CH2CONH2)CH2CO2- (R = H, L3; Me, L4) which have in-plane 2N(amine,) 2 O(carboxylate) ligands at pH 6 undergo amide group deprotonation in basic solution to give CuN(amine)2N- (amide)2 chromophores resulting from the displacement of the in-plane carboxylate ligands by the superior sigma-donating, deprotonated, amide nitrogens. The concentration pK(a) values for the deprotonations at 25-degrees-C, l = 0.1 mol dm-3 are 9.19 +/- 0.02 and 9.87 +/- 0.02 for [CuL3], and 8.60 +/- 0.02 and 9.81 +/- 0.02 for [CuL4]. The unexpectedly large differences in the first pK(a) values is attributed to a steric interaction between the methyl substituent and an axially co-ordinated CH2CONH2 group, in the complex of L4 which is relieved as a result of the first ionisation step.",
keywords = "peptides, agents, hydrolysis products , anticancer agent",
author = "DAEID, {N N} and NOLAN, {K B} and RYAN, {L P}",
year = "1991",
month = "9",
doi = "10.1039/DT9910002301",
language = "English",
pages = "2301--2304",
journal = "Journal of the Chemical Society, Dalton Transactions",
issn = "0300-9246",
number = "9",

}

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T1 - Copper(II) complexes of hydrolysis products of the anticancer bis(3,5-dioxopiperazin-1-yl)alkanes. Displacement of co-ordinated carboxylate ligands by deprotonated amide groups in basic solution

AU - DAEID, N N

AU - NOLAN, K B

AU - RYAN, L P

PY - 1991/9

Y1 - 1991/9

N2 - The copper(II) complexes of the diacid diamide -O2CCH2(H2NOCCH2)NCH2CHRN(CH2CONH2)CH2CO2- (R = H, L3; Me, L4) which have in-plane 2N(amine,) 2 O(carboxylate) ligands at pH 6 undergo amide group deprotonation in basic solution to give CuN(amine)2N- (amide)2 chromophores resulting from the displacement of the in-plane carboxylate ligands by the superior sigma-donating, deprotonated, amide nitrogens. The concentration pK(a) values for the deprotonations at 25-degrees-C, l = 0.1 mol dm-3 are 9.19 +/- 0.02 and 9.87 +/- 0.02 for [CuL3], and 8.60 +/- 0.02 and 9.81 +/- 0.02 for [CuL4]. The unexpectedly large differences in the first pK(a) values is attributed to a steric interaction between the methyl substituent and an axially co-ordinated CH2CONH2 group, in the complex of L4 which is relieved as a result of the first ionisation step.

AB - The copper(II) complexes of the diacid diamide -O2CCH2(H2NOCCH2)NCH2CHRN(CH2CONH2)CH2CO2- (R = H, L3; Me, L4) which have in-plane 2N(amine,) 2 O(carboxylate) ligands at pH 6 undergo amide group deprotonation in basic solution to give CuN(amine)2N- (amide)2 chromophores resulting from the displacement of the in-plane carboxylate ligands by the superior sigma-donating, deprotonated, amide nitrogens. The concentration pK(a) values for the deprotonations at 25-degrees-C, l = 0.1 mol dm-3 are 9.19 +/- 0.02 and 9.87 +/- 0.02 for [CuL3], and 8.60 +/- 0.02 and 9.81 +/- 0.02 for [CuL4]. The unexpectedly large differences in the first pK(a) values is attributed to a steric interaction between the methyl substituent and an axially co-ordinated CH2CONH2 group, in the complex of L4 which is relieved as a result of the first ionisation step.

KW - peptides

KW - agents

KW - hydrolysis products

KW - anticancer agent

U2 - 10.1039/DT9910002301

DO - 10.1039/DT9910002301

M3 - Article

SP - 2301

EP - 2304

JO - Journal of the Chemical Society, Dalton Transactions

T2 - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

SN - 0300-9246

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ER -