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

Kuppert, Dirk; Sander, Jürgen; Roth, Christian; Wörle, Michael; Weyhermüller, Thomas; Reiß, Guido J.; Schilde, Uwe; Müller, Iris M.; Hegetschweiler, Kaspar

doi:10.1002/1099-0682(200109)2001:10<2525::aid-ejic2525>3.0.co;2-z

Cited by 17 publications

(11 citation statements)

References 37 publications

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“…1964, 36, 1698 The characteristic pH-dependence of the diaminoethylene H(-C) resonances was used to estimate the ratio of tautomers for (HMeL a ) þ and (H 2 MeL a ) 2þ (calculations for the CH 2 groups in β-position to NH 2 exhibited very similar shifts for the different tautomers and are thus not suited for such an analysis). The deshielding constants C(R) = 0.633 ppm, C(R) = 9C(γ) and C(β) = 5C(γ), which were derived from the fully protonated (H 3 MeL a ) 3þ and the deprotonated MeL a , 6,7,45 revealed amounts of 42% and 95% for a protonation of the primary amino group in (HMeL a ) þ and in (H 2 MeL a ) 2þ , respectively. significant.…”

Section: Resultsmentioning

confidence: 99%

“…1 H and 13 C{ 1 H} NMR spectra were measured in D 2 O (294 K, Bruker DRX Avance 400 MHz NMR spectrometer, resonance frequencies: 400.13 MHz for 1 H and 100. 6 MHz for 13 C). Chemical shifts are given in ppm relative to D 4 -sodium (trimethylsilyl)propionate as internal standard (δ = 0 ppm).…”

Section: Methodsmentioning

confidence: 99%

“…The different reactivity of the primary and secondary amino groups opens new routes to a selective derivatization, rendering such intermediate types particularly versatile. 6,8 In a recent paper, 8 entitled "First-Transition-Metal Complexes Containing the Ligands 6-Amino-6-methylperhydro-1,4-diazepine (AAZ) and a New Functionalized Derivative: Can AAZ Act as a Mimetic Ligand for 1,4,7-Triazacyclononane? ", arguments were provided for using diazepane-based triamines as a promising source for new tailored metalcomplexing agents.…”

Section: Introductionmentioning

confidence: 99%

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Facially Coordinating Triamine Ligands with a Cyclic Backbone: Some Structure−Stability Correlations

et al. 2010

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Metal complex formation of the two cyclic triamines 6-methyl-1,4-diazepan-6-amine (MeL(a)) and all-cis-2,4,6-trimethylcyclohexane-1,3,5-triamine (Me(3)tach) was studied. The structure of the free ligands (H(x)MeL(a))(x+) and H(x)Me(3)tach(x+) (0 ≤ x ≤ 3) was investigated by pH-dependent NMR spectroscopy and X-ray diffraction experiments. The crystal structure of (H(2)Me(3)tach)(p-O(3)S-C(6)H(4)-CH(3))(2) showed a chair conformation with axial nitrogen atoms for the doubly protonated species. In contrast to a previous report, Me(3)tach was found to be a stronger base than the parent cis-cyclohexane-1,3,5-triamine (tach); pK(a)-values of H(3)Me(3)tach(3+) (25 °C, 0.1 M KCl): 5.2, 7.4, 11.2. The crystal structures of (H(3)MeL(a))(BiCl(6))·2H(2)O and (H(3)MeL(a))(ClO(4))Cl(2) exhibited two distinct twisted chair conformations of the seven membered diazepane ring. [Co(MeL(a))(2)](3+) (cis: 1(3+), trans: 2(3+)), trans-[Fe(MeL(a))(2)](3+) (3(3+)), [(MeL(a))ClCd(μ(2)-Cl)](2) (4), trans-[Cu(MeL(a))(2)](2+) (5(2+)), and [Cu(HMeL(a))Br(3)] (6) were characterized by single crystal X-ray analysis of 1(ClO(4))(3)·H(2)O, 2Br(3)·H(2)O, 3(ClO(4))(3)·0.8MeCN·0.2MeOH, 4, 5Br(2)·0.5MeOH, and 6·H(2)O. Formation constants and redox potentials of MeL(a) complexes were determined by potentiometric, spectrophotometric, and cyclovoltammetric measurements. The stability of [M(II)(MeL(a))](2+)-complexes is low. In comparison to the parent 1,4-diazepan-6-amine (L(a)), it is only slightly enhanced. In analogy to L(a), MeL(a) exhibited a pronounced tendency for forming protonated species such as [M(II)(HMeL(a))](3+) or [M(II)(MeL(a))(HMeL(a))](3+) (see 6 as an example). In contrast to MeL(a), Me(3)tach forms [M(II)L](2+) complexes (M = Cu, Zn) of very high stability, and the coordination behavior corresponds mainly to an "all-or-nothing" process. Molecular mechanics calculations showed that the low stability of L(a) and MeL(a) complexes is mainly due to a large amount of torsional strain within the pure chair conformation of the diazepane ring, required for tridentate coordination. This behavior is quite contrary to Me(3)tach and tacn (tacn =1,4,7-triazacyclononane), where the main portion of strain is already preformed in the free ligand, and the amount, generated upon complex formation, is comparably low.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Facially Coordinating Triamine Ligands with a Cyclic Backbone: Some Structure−Stability Correlations

et al. 2010

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“…The secondary amino group has limited coordination flexibility as compared to the primary amino groups and therefore constructs a tridentate coordination plane coplanar to the rigid backbone. cis -Tach is a μ-3 ligand with the third, in this case primary, amino group extended away from the cyclohexane ring. This confers a significant amount of flexibility as the torsion angle along the C−N bonds can be distorted upon coordination.…”

Section: Resultsmentioning

confidence: 99%

Coordination Networks through the Dimensions: From Discrete Clusters to 1D, 2D, and 3D Silver(I) Coordination Polymers with Rigid Aliphatic Amino Ligands

2004

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The use of a ligand directed strategy in the assembly of discrete clusters, 1D chains, 2D layers, and 3D networks using aliphatic N-donor ligands has been investigated. The ligands are a family of amines with rigid backbones [cis,cis-1,3,5-triaminocyclohexane (cis-tach), cis,trans-1,3,5-triaminocyclohexane (trans-tach), cis-1,3-diaminocyclohexane (cis-dach), and cis-3,5-diaminopiperidine (cis-dapi)], and their complexation with Ag(I) salts results in a diverse set of architectures with the following compositions: [Ag3(cis-tach)2]F3.4CH(3)OH.0.5H2O (1), [Ag3(cis-tach)2]F3.6H2O (2), ([Ag(cis-dach)]ClO4)n (3), ([Ag(cis-tach)]NO3)n (4), ([Ag(trans-tach)]PF6)n(5), and ([Ag(cis-dapi)]CF3SO3)n (6). Structural analysis shows that compounds 1 and 2 are discrete M(3)L(2) cage-type clusters with varying solvent molecule content. Short Ag...Ag contacts (3.021(8) A) are observed to dimerize discrete units in compound 2. Compound 3 is a 1D zigzag chain formed by coordination to the two primary amines of cis-dach, whereas the tridentate ligands in compounds 4 and 5 (cis-tach and trans-tach, respectively) are able to form tubular architectures by virtue of their ability to "wrap" round the channel walls. An infinite 2D coordination network is demonstrated by compound 6, in which the three coplanar amino donors of cis-dapi coordinate to the trigonal planar Ag(I) ions to form a layered structure of 6(3) topology. These are compared with a previously reported 3D structure, ([Ag(trans-tach)]NO3)n (7), that belongs to this family of architectures.

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“…The V−tdci system was investigated by three independent batches with total vanadium to total tdci molar ratios of 1:2, 1:3, and 1:4. Each sample of the 1:3 V−tdci batch was also investigated spectrophotometrically (350−700 nm) …”

Section: Methodsmentioning

confidence: 99%

Complex Formation of Vanadium(IV) with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol and Related Ligands

Morgenstern¹,

Steinhauser²,

Hegetschweiler³

et al. 2004

Inorg. Chem.

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The complex formation of vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci) was studied in aqueous solution and in the solid state. The formation constants of [V(IV)O(taci)](2+), [V(IV)O(tdci)](2+), and [V(IV)(tdci)(2)](4+) and of the deprotonation product [V(IV)(tdci)(2)H(-)(1)](3+) were determined (25 degrees C, 0.1 M KNO(3)). Cyclic voltammetry measurements established a reversible one-electron transfer for the [V(IV)(tdci)(2)H(-)(m)]((4)(-)(m))/[V(III)(tdci)(2)H(-)(n)]((3)(-)(n)) couple (0

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

Cited by 17 publications

References 37 publications

Facially Coordinating Triamine Ligands with a Cyclic Backbone: Some Structure−Stability Correlations

Facially Coordinating Triamine Ligands with a Cyclic Backbone: Some Structure−Stability Correlations

Coordination Networks through the Dimensions: From Discrete Clusters to 1D, 2D, and 3D Silver(I) Coordination Polymers with Rigid Aliphatic Amino Ligands

Complex Formation of Vanadium(IV) with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol and Related Ligands

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