The coordination chemistry of cis-3,5-diaminopiperidine and substituted derivatives

Jörg W. Pauly; Jürgen Sander; Dirk Kuppert; Manuela Winter; Guido J. Reiss; Fabio Zürcher; Rudolf Hoffmann; Thomas F. Fässler; Kaspar Hegetschweiler

doi:10.1002/1521-3765(20000804)6:15<2830::AID-CHEM2830>3.0.CO;2-X

The coordination chemistry of cis-3,5-diaminopiperidine and substituted derivatives

Jörg W. Pauly
, Jürgen Sander
, Dirk Kuppert
, Manuela Winter
, Guido J. Reiss
, Fabio Zürcher
, Rudolf Hoffmann
, Thomas F. Fässler
, Kaspar Hegetschweiler

Saarland University
Max-Planck-lnstitut für Kohlenforschung
Heinrich-Heine-University
ETH Zurich

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

29 Scopus citations

Abstract

An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with Co(II). Co(III), Ni(II), Cu(II), Zn(II), and Cd(II) has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for Ni(II) (logβ₂ = 21.2,β₂ = [M(dapi)₂][M]^-1[dapi]^-2, 25°C, μ = 0.1 mol dm^-3). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)₂]³⁺ with a redox potential of 0.91V (versus NHE) for the Ni(II/III) couple. [Co(dapi)₂]³⁺ was prepared by aerial oxidation of the corresponding Co(II) precursor. The two isomers trans-[Co(dapi)₂]³⁺ (1³⁺, 26%) and cis-[Co(dapi)₂]³⁺ (2³⁺, 74%), have been separated and isolated as solid C1^- and CF₃SO₃^- salts. In a non-aqueous medium 1³⁺ and 2³⁺ reacted with paraformaldehyde and NEt₃ to give the methylidene-imino derivatives 3³⁺ and 4³⁺, in which the two piperidine rings are bridged by two or one N-CH₂-O-CH₂ N bridges, respectively. Crystal structure analyses were performed for H₃da-pi[ZnCl₄]Cl, 1CI₃·2H₂O, 2Cl₃·H₂O, 3[ZnCl₄]Cl, 4[ZnCl₄]Cl, [Ni(dapi)₂]Cl₂. H₂O, [Cu(dapi)₂](NO₃)₂, [Cu(dapi)Cl₂], [(dapi)ClCd-(μ2-Cl)₂-CdCl(dapi)], and [Co(dapi)(NO₂)(CO₃)]. The stability of [M(II)(dapi)]²⁺ and [M(II)(dapi)₂]²⁺ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]²⁺ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The Ni¹¹ complexes of the pentadentate N³,N⁵-bis-(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py₂dapi) and the hexadentate N³,N⁵,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py₃dapi) have been isolated as crystalline ClO₄^- salts [Ni-(py₂dapi)Cl]ClO₄ and [Ni(py₃dapi)]-(ClO₄)₂· H₂O and characterized by crystal structure analyses.

Original language	English
Pages (from-to)	2830-2846
Number of pages	17
Journal	Chemistry - A European Journal
Volume	6
Issue number	15
DOIs	https://doi.org/10.1002/1521-3765(20000804)6:15<2830::AID-CHEM2830>3.0.CO;2-X
State	Published - 4 Aug 2000
Externally published	Yes

Keywords

N ligands
Polyamines
Stability constants
Structure elucidation

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10.1002/1521-3765(20000804)6:15<2830::AID-CHEM2830>3.0.CO;2-X

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@article{27a3f556120e4047a9b95df41285c63e,

title = "The coordination chemistry of cis-3,5-diaminopiperidine and substituted derivatives",

abstract = "An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with Co(II). Co(III), Ni(II), Cu(II), Zn(II), and Cd(II) has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for Ni(II) (logβ2 = 21.2,β2 = [M(dapi)2][M]-1[dapi]-2, 25°C, μ = 0.1 mol dm-3). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding Co(II) precursor. The two isomers trans-[Co(dapi)2]3+ (13+, 26\%) and cis-[Co(dapi)2]3+ (23+, 74\%), have been separated and isolated as solid C1- and CF3SO3- salts. In a non-aqueous medium 13+ and 23+ reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 33+ and 43+, in which the two piperidine rings are bridged by two or one N-CH2-O-CH2 N bridges, respectively. Crystal structure analyses were performed for H3da-pi[ZnCl4]Cl, 1CI3·2H2O, 2Cl3·H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2. H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(μ2-Cl)2-CdCl(dapi)], and [Co(dapi)(NO2)(CO3)]. The stability of [M(II)(dapi)]2+ and [M(II)(dapi)2]2+ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]2+ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The Ni11 complexes of the pentadentate N3,N5-bis-(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py2dapi) and the hexadentate N3,N5,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py3dapi) have been isolated as crystalline ClO4- salts [Ni-(py2dapi)Cl]ClO4 and [Ni(py3dapi)]-(ClO4)2· H2O and characterized by crystal structure analyses.",

keywords = "N ligands, Polyamines, Stability constants, Structure elucidation",

author = "Pauly, \{J{\"o}rg W.\} and J{\"u}rgen Sander and Dirk Kuppert and Manuela Winter and Reiss, \{Guido J.\} and Fabio Z{\"u}rcher and Rudolf Hoffmann and F{\"a}ssler, \{Thomas F.\} and Kaspar Hegetschweiler",

year = "2000",

month = aug,

day = "4",

doi = "10.1002/1521-3765(20000804)6:15<2830::AID-CHEM2830>3.0.CO;2-X",

language = "English",

volume = "6",

pages = "2830--2846",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

number = "15",

}

TY - JOUR

T1 - The coordination chemistry of cis-3,5-diaminopiperidine and substituted derivatives

AU - Pauly, Jörg W.

AU - Sander, Jürgen

AU - Kuppert, Dirk

AU - Winter, Manuela

AU - Reiss, Guido J.

AU - Zürcher, Fabio

AU - Hoffmann, Rudolf

AU - Fässler, Thomas F.

AU - Hegetschweiler, Kaspar

PY - 2000/8/4

Y1 - 2000/8/4

N2 - An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with Co(II). Co(III), Ni(II), Cu(II), Zn(II), and Cd(II) has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for Ni(II) (logβ2 = 21.2,β2 = [M(dapi)2][M]-1[dapi]-2, 25°C, μ = 0.1 mol dm-3). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding Co(II) precursor. The two isomers trans-[Co(dapi)2]3+ (13+, 26%) and cis-[Co(dapi)2]3+ (23+, 74%), have been separated and isolated as solid C1- and CF3SO3- salts. In a non-aqueous medium 13+ and 23+ reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 33+ and 43+, in which the two piperidine rings are bridged by two or one N-CH2-O-CH2 N bridges, respectively. Crystal structure analyses were performed for H3da-pi[ZnCl4]Cl, 1CI3·2H2O, 2Cl3·H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2. H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(μ2-Cl)2-CdCl(dapi)], and [Co(dapi)(NO2)(CO3)]. The stability of [M(II)(dapi)]2+ and [M(II)(dapi)2]2+ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]2+ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The Ni11 complexes of the pentadentate N3,N5-bis-(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py2dapi) and the hexadentate N3,N5,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py3dapi) have been isolated as crystalline ClO4- salts [Ni-(py2dapi)Cl]ClO4 and [Ni(py3dapi)]-(ClO4)2· H2O and characterized by crystal structure analyses.

AB - An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with Co(II). Co(III), Ni(II), Cu(II), Zn(II), and Cd(II) has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for Ni(II) (logβ2 = 21.2,β2 = [M(dapi)2][M]-1[dapi]-2, 25°C, μ = 0.1 mol dm-3). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding Co(II) precursor. The two isomers trans-[Co(dapi)2]3+ (13+, 26%) and cis-[Co(dapi)2]3+ (23+, 74%), have been separated and isolated as solid C1- and CF3SO3- salts. In a non-aqueous medium 13+ and 23+ reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 33+ and 43+, in which the two piperidine rings are bridged by two or one N-CH2-O-CH2 N bridges, respectively. Crystal structure analyses were performed for H3da-pi[ZnCl4]Cl, 1CI3·2H2O, 2Cl3·H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2. H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(μ2-Cl)2-CdCl(dapi)], and [Co(dapi)(NO2)(CO3)]. The stability of [M(II)(dapi)]2+ and [M(II)(dapi)2]2+ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]2+ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The Ni11 complexes of the pentadentate N3,N5-bis-(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py2dapi) and the hexadentate N3,N5,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py3dapi) have been isolated as crystalline ClO4- salts [Ni-(py2dapi)Cl]ClO4 and [Ni(py3dapi)]-(ClO4)2· H2O and characterized by crystal structure analyses.

KW - N ligands

KW - Polyamines

KW - Stability constants

KW - Structure elucidation

UR - https://www.scopus.com/pages/publications/0034604429

U2 - 10.1002/1521-3765(20000804)6:15<2830::AID-CHEM2830>3.0.CO;2-X

DO - 10.1002/1521-3765(20000804)6:15<2830::AID-CHEM2830>3.0.CO;2-X

M3 - Article

AN - SCOPUS:0034604429

SN - 0947-6539

VL - 6

SP - 2830

EP - 2846

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 15

ER -

The coordination chemistry of cis-3,5-diaminopiperidine and substituted derivatives

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Keywords

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