Ligand Synthesis and Metal Complex Formation of 1,2,3-Triaminopropane

Zimmer, Anja; Müller, Iris M.; Reiß, Guido J.; Caneschi, Andrea; Gatteschi, Dante; Hegetschweiler, Kaspar

doi:10.1002/(sici)1099-0682(199812)1998:12<2079::aid-ejic2079>3.0.co;2-b

Cited by 15 publications

(20 citation statements)

References 32 publications

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“…A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The Ni II complexes of the pentadentate N 3 ,N 5 -bis-(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py 2 dapi) and the hexadentate N 3 ,N 5 ,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py 3 dapi) have been isolated as crystalline ClO 4 À salts [Ni-(py 2 dapi)Cl]ClO 4 and [Ni(py 3 …”

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The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

et al. 2000

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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 CoII, CoIII, NiII, CuII, ZnII, and CdII 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 NiII (log beta2 = 21.2, beta2 = [M(dapi)2][M](-1)[dapi](-2), 25 degrees C, mu = 0.1 mol dm(-3)). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91 V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding CoII precursor. The two isomers trans-[Co(dapi)2]3+ (1(3+), 26%) and cis-[Co(dapi)2]3+ (2(3+), 74%), have been separated and isolated as solid Cl- and CF3SO3- salts. In a non-aqueous medium 1(3+) and 2(3+) reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 3(3+) and 4(3+), 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 H3dapi[ZnCl4]Cl, 1Cl3 x 2H2O, 2Cl3 x H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2 x H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(mu2-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 NiII 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 x H2O and characterized by crystal structure analyses.

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The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

et al. 2000

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“…Comparison of formation constants for Cu II -and Ni II (amine) complexes; the linear free-energy relationship (squares) for selected diamines (log β 2 ), triamines H 2 NϪ(CH 2 ) x ϪNHϪ CH 2 ) y ϪNH 2 (log β 1 ), and tetraamines H 2 NϪ(CH 2 ) x ϪNHϪ (CH 2 ) y ϪNHϪ(CH 2 ) z ϪNH 2 (log β 1 ) is log β Ni ϭ 0.77 ϫ log β Cu Ϫ 1.84; this is compared with log β 2 values of the potentially tripodal ligands cis-dap, dapi, and tmca (circles); the data are from refs. [5,25,27] and from this work (Tables 2 and 3 This effect would be incompatible with a significant interaction between the third amino group and the metal cation. It is also noteworthy that the pK a values of [Cu(HL) 2 ] 4ϩ are very similar for L ϭ cis-dap and L ϭ trans-dap (7.1, 7.7 versus 6.8, 7.5, respectively).…”

Section: Equilibria In Aqueous Solutionmentioning

confidence: 63%

“…Similarly, the bis(complexes) [CuH x L 2 ] (2ϩx)ϩ (0 Յ x Յ 2, L ϭ cis-dap, trans-dap; and x ϭ 0, L ϭ cis-cptn) all show a characteristic band in their visible spectra with an absorption maximum at 550Ϫ570 nm (Table 6). These values are [a] Abbreviation of ligands and references: cis-dap ϭ cis-3,4-diaminopyrrolidine; trans-dap ϭ trans-diaminopyrrolidine; trap ϭ 1,2,3-propanetriamine; [27] tmca ϭ all-cis-2,4,6-trimethoxycyclohexane-1,3,5-triamine; [28] dapi ϭ cis-3,5-piperidinediamine; [5] cis-cptn ϭ cis-cyclopentane-1,2-diamine; trans-cptn ϭ trans-cyclopentane-1,2-diamine; cis-chxn ϭ cis-cyclohexane-1,2-diamine; [26] trans-chxn ϭ trans-cyclohexane-1,2-diamine; [26] ampy ϭ 3-aminopyrrolidine; en ϭ ethane-1,2-diamine [26] . indicative of a trans (square-planar) CuN 4 chromophore with additional loosely bound water molecules at the apices.…”

Section: Equilibria In Aqueous Solutionmentioning

confidence: 99%

“…The ligand trap, by analogy with cis-dap, forms similar protonated Cu complexes in acidic solution, and a bridging mode with bidentate and monodentate coordination has been established from the crystal structure of [Cu-(trap) 2 ]Cl 2 . [27] However, it appears that the locked conformation is not optimal for metal binding: The trap complexes are generally more stable than the corresponding cis-dap analogues. Moreover, with other metal cations such as Ni II , the flexibility of trap allows tridentate coordination, which is not accessible for cis-dap.…”

Section: Structural Aspects Of the Metal Complexesmentioning

confidence: 99%

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The Coordination Chemistry ofcis-3,4-Diaminopyrrolidine and Related Polyamines

Kuppert

Sander

Roth

et al. 2001

Eur. J. Inorg. Chem.

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cptn) have been prepared in multigram quantities. The complexation of these ligands and of 3-aminopyrrolidine (ampy) with Ni II , Cu II , Zn II , and Cd II has been studied in solution by means of potentiometric and spectrophotometric titrations. The complexes of the triamines cis-dap and trans-dap show a pronounced tendency to form protonated species such as [M II (HL)] 3+ , [M II (HL) 2 ] 4+ , and [M II (HL)L] 3+ , indicative of a bidentate coordination mode of the ligand L. The UV/Vis spectra of the corresponding Cu II complexes further confirmed bidentate coordination with trans-CuN 4 geometry. The overall stabilities of the bis complexes [ML 2 ] 2+ decrease in the order ciscptn Ͼ cis-dap Ͼ trans-cptn Ͼ ampy Ͼ trans-dap. The considerably lower stabilities of the ampy complexes as compared to the corresponding cis-dap complexes indicate metal binding to the two primary amino groups of the latter

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“…18,19 In such systems, the transition metal complexes can play many roles, because of their wide variety of structural, electronic, redox and catalytic properties. [20][21][22][23][24][25][26] In particular, the coordination of ruthenium complexes to meso-pyridylporphyrins has provided rather versatile systems, in which the chemical and photochemical reactivity can be modulated by the electronic, structural and steric effects induced by the peripheral complexes. [27][28][29][30][31][32] However, it should be noticed that in the case of tetrapyridyl porphyrins, the electronic coupling between the porphyrin center and the ruthenium complexes is mediated by a Matsumoto et al 729 Vol.…”

Section: Introductionmentioning

confidence: 99%

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

Matsumoto

Toyama

Mayer

et al. 2009

J. Braz. Chem. Soc.

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Uma nova espécie cobre(II)-tetra(3,4-piridil)porfirazina tetrarrutenada, [CuTRPyPz] 4+ foi sintetizada e sua caracterização conduzida por meio de métodos analíticos, espectroscópicos e eletroquímicos. Sua extensa conjugação-π a distingue dos derivados análogos da mesotetrapiridilporfirina, levando à ocorrência de interações eletrônicas mais fortes entre os complexos periféricos e o anel porfirazínico central. Com base nas interações eletrostáticas e de empilhamento-π, foram realizadas montagens, camada-por-camada, de filmes funcionais, combinando-se a [CuTRPyPz] 4+ com a ftalocianina de cobre(II) tetrassulfonada, [CuTSPc] 4−. As propriedades condutoras e eletrocatalíticas desses filmes foram investigadas através de técnicas de impedância e de voltametria de disco rotatório, observando-se um comportamento metálico nas proximidades do potencial do par redox Ru(III)/(II), bem como uma pronunciada atividade catalítica na oxidação de íons nitrito e sulfito, em meio aquoso.A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz] 4+ , has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This π-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable π-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz] 4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc] 4− . Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.Keywords: molecular conductors, porphyrazines, ruthenium polypyridines, thin films, electrocatalysis IntroductionPhthalocyanines and porphyrins are important macrocyclic compounds exhibiting a wide variety of applications in science and technology. [1][2][3][4][5][6][7][8][9][10][11][12][13] Their main characteristics are associated with the π-conjugated ring which imparts interesting physical and chemical properties, including the facility of stacking and yielding molecular films. The possibility of rationally manipulating their properties at the nanoscale is a relevant issue to be pursued, aiming the generation of functional molecular materials for nanotechnology devices. [14][15][16][17] As a matter of fact, tetrapyridyl porphyrins have already been modified with transition metal complexes in order to generate convenient building-blocks and connectors for assembling supramolecular systems and nanostructured materials. 18,19 In such systems, the transition metal complexes can play many roles, because of their wide variety of structural, electronic, redox and catalytic properties. [20][21][22][23][24][25][26] In particular, the coordinati...

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Ligand Synthesis and Metal Complex Formation of 1,2,3-Triaminopropane

Cited by 15 publications

References 32 publications

The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

The Coordination Chemistry ofcis-3,4-Diaminopyrrolidine and Related Polyamines

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

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