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Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination.

ABSTRACT: For decades, the planarity of the amide functional group has garnered sustained interest in organic chemistry, enticing chemists to deform its usually characteristic high-fidelity plane. As opposed to the construction of amides that are distorted by imposing rigid covalent bond assemblies, we demonstrate herein the deformation of the amide plane through increased steric bulk in the periphery of the amide moiety, which is induced by coordination to metal cations. A crystallographic analysis revealed that the thus obtained amides exhibit significant pyramidalization and twisting upon coordination to the metals, while the amide functional group remained intact. The observed deformation, which should be attributed to through-space interactions, substantially enhanced the solvolytic cleavage of the amide, providing compelling evidence that temporary crowding in the periphery of the amide functional group may be used to control the reactivity of amides.

SUBMITTER: Adachi S

PROVIDER: S-EPMC5304688 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature

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Pyramidalization/twisting of the amide functional group <i>via</i> remote steric congestion triggered by metal coordination.

Adachi Shinya S Kumagai Naoya N Shibasaki Masakatsu M

Chemical science 20160923 1

For decades, the planarity of the amide functional group has garnered sustained interest in organic chemistry, enticing chemists to deform its usually characteristic high-fidelity plane. As opposed to the construction of amides that are distorted by imposing rigid covalent bond assemblies, we demonstrate herein the deformation of the amide plane through increased steric bulk in the periphery of the amide moiety, which is induced by coordination to metal cations. A crystallographic analysis revea ...[more]

PMID: 28451151

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Project description:Ten coordination polymers constructed from divalent metal salts, polycarboxylic acids, and bis-pyridyl-bis-amide ligands with different donor atom positions and flexibility are reported. They were structurally characterized by single-crystal X-ray diffraction. The ten coordination polymers are as follows: (1) {[Ni(L¹)(3,5-PDA)(H₂O)₃]·2H₂O}n (L¹ = N,N'-di(3-pyridyl)suberoamide, 3,5-H₂PDA = 3,5-pyridinedicarboxylic acid); (2) {[Ni₂(L¹)₂(1,3,5-HBTC)₂(H₂O)₄]·H₂O}n (1,3,5-H₃BTC = 1,3,5-benzenetricarboxylic acid); (3) {[Ni(L²)(5-tert-IPA)(H₂O)₂]·2H₂O}n (L² = N,N'-di(3-pyridyl)adipoamide, 5-tert-H₂IPA = 5-tert-butylisophthalic acid); (4) [Ni(L³)1.5(5-tert-IPA)]n (L³ = N,N'-di(4-pyridyl)adipoamide); (5) [Co(L¹)(1,3,5-HBTC)(H₂O)]n; (6) {[Co₃(L¹)₃(1,3,5-BTC)₂(H₂O)₂]·6H₂O}n; (7) [Cu(L⁴)(AIPA)]n (L⁴ = N,N'-bis(3-pyridinyl)terephthalamide, H₂AIPA = 5-acetamido isophthalic acid); (8) {[Cu(L²)0.5(AIPA)]·MeOH}n; (9) {[Zn(L⁴)(AIPA)]·2H₂O}n; and (10) {[Zn(L²)(AIPA)]·2H₂O}n. Complex 1 forms a 1D chain and 2 is a two-fold interpenetrated 2D layer with the sql topology, while 3 is a 2D layer with the hcp topology and 4 shows a self-catenated 3D framework with the rare (4²·6⁷·8)-hxg-d-5-C2/c topology. Different Co/1,3,5-H₃BTC ratios were used to prepare 5 and 6, affording a 2D layer with the sql topology and a 2D layer with the (4·8⁵)₂(4)₂(8³)₂(8) topology that can be further simplified to an hcp topology. While complex 7 is a 2D layer with the (4²·6⁷·8)(4²·6)-3,5L2 topology and 8 is a 2-fold interpenetrated 3D framework with the pcu topology, complexes 9 and 10 are self-catenated 3D frameworks with the (424·6⁴)-8T2 and the (4⁴·610·8)-mab topologies, respectively. The effects of the identity of the metal center, the ligand isomerism, and the flexibility of the spacer ligands on the structural diversity of these divalent coordination polymers are discussed. The luminescent properties of 9 and 10 and their photocatalytic effects on the degradation of dyes are also investigated.

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Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination.

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Pyramidalization/twisting of the amide functional group <i>via</i> remote steric congestion triggered by metal coordination.

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