The Reactions of Coordinated Ligands

Busch, Daryle H.; Burke, John A.; Jicha, Donald C.; Thompson, M.C.; Morris, Melvin L.

doi:10.1021/ba-1963-0037.ch008

Cited by 30 publications

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“…The same product can be obtained under similar reaction conditions in the presence of Et 4 NOH instead of Et 3 N. The reaction seemed to be scalable to a certain extent [3 times the reactants and solvents, the purity was confirmed by pxrd studies] beyond which single‐crystals of 1 were obtained within powders. Having the crystal structure of 1 at hand, we aimed at the isolation of the transformed ligand (H 4 L 2 ), a method that usually is not common in other systems where metal‐assisted ligand transformations have been observed, mainly because such “transformed” species may not be stable when isolated from their metal complexes . Both IR (Figure S2) and 1 HNMR (Figure S3) spectra of the H 4 L 2 were different than those obtained from H 6 L 1 as we were expecting.…”

Section: Resultsmentioning

confidence: 99%

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An I²O¹ Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

2018

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The use of 4,4′‐[oxalylbis(azanediyl)]bis(2‐hydroxybenzoic acid) (H6L1) in the Ba2+ chemistry has afforded a 3D polymer, namely [Ba(H2L2)(H2O)]n (1), which is based on H2L22– anions derived by the in‐situ metal‐assisted transformation of H6L1. The neutral H4L2 [4‐(carboxyformamido)‐2‐hydroxybenzoic acid] ligand was isolated from 1 and characterized by spectroscopic methods. Polymer 1 is based on edge and face‐sharing BaO10 polyhedra which create an inorganic layer pillared to the third dimension by the organic ligands and has been classified as an I2O1 framework. The topological analysis of 1 provided an opportunity to introduce a method for the deconstruction of I2O1 frameworks by adopting principles applied in the deconstruction of Metal‐Organic‐Frameworks (MOFs) with rod Secondary Building Units (SBUs). A detailed discussion and insights for the proper use of the ImOn notation which finds application in describing the dimensionality in MOFs, is also provided.

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Section: Resultsmentioning

confidence: 99%

“…In‐situ metal‐assisted ligand transformations are known since the early stages of the development of coordination chemistry . The electronic properties of an organic ligand that interacts with a metal ion are altered such that the ligand may become susceptible to reactions that would not be otherwise expected , .…”

Section: Introductionmentioning

confidence: 99%

An I²O¹ Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

2018

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“…Every chemistry student has heard the story and it resides in our memories. 16a) [9, 11,34]. Therefore, if a ligand molecule having four ligating atoms were able to react with itself, ring closure might be greatly favored by letting First Considerations: Principles, Classification, and History the molecule wrap itself around a metal ion (Fig.…”

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confidence: 99%

“…It was suggested that the hydrogen bonding pat- 32 D. H. Busch Reaction leading to discovery of the HVL template by Hunter [166]. 34 Effect of substituents on the isomer distribution in catenane synthesis using the HVL template [166]. Although the templating must be quite different, it seems appropriate to reflect on another case of serendipitous catenane synthesis [85].…”

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confidence: 99%

First Considerations: Principles, Classification, and History

Busch

2005

Topics in Current Chemistry

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“…similarly illustrated by the fact that only unbridged coordinated mercaptides act as vigorous nucleophiles.Equation 27 shows the resulting distinction between bridged and terminal groups(27) by means of their reactions with alkyl halides.…”

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Metal Ion Control of Chemical Reactions

Busch

1971

Science

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In seeking to elaborate the ways in which metal ions may affect chemical reactions, it seems useful to classify first according to the intimacy of the interaction between metal atom and reactants. Three levels of interaction are evident. In many processes the metal ion serves to alter the character of the medium by changing ionic strength, solvent structuring or destructuring, and possibly other characteristics of the medium, all of which require only longrange interaction between metal ion and reactant. These influences are left for others to treat. In this article attention is focused on metal ion effects at two more intimate levels of interaction. In the second category of interaction the metal ion serves as a reactant. Rather than merely determining the environment within which a given process occurs (the first category), the metal ion in this case is a projectile which produces reaction when it encounters the substrate. The morphological criterion for this category of effect is the initiation of chemical reaction upon contact between substrate and metal. Finally, the third level of interaction involves prior association of the metal ion with a substrate that is to undergo subsequent reaction, either unimolecularly or upon encounter with suitable reagents. 'The author is professor of chemistry at Ohio State University, Columbus 43210. JANUARY 1971Here the metal ion is a it is precisely by exam category of interaction 1 of metal ion influences ( actions are most readily Much attention is giv subject of homogeneous ticularly in processes i ions and metal complexe many enzymes that ar metal ions may be inclu heading. Clearly, those are truly activated by n be describable in term! both of the categories o fects stated here, that derivatives as reagents moieties as substituents. with a single-step proces, be used to delineate a p ion capability, catalytic of necessity, multistep X recycling of the catalyst catalytic reaction must i two steps. These minimu encounter and alteratioi strate of interest by the and (ii) restoration of 1 its original condition. F complex-forming process tance, and homogeneou volving metal ion catalys quire at least three cle steps: (i) in a first step ti coordinates to a substi either with or without alt SCIE:NCE: substrate; (ii) the complex then encounters a reagent and undergoes chemical change; (iii) thereafter, the complex is disassembled and the metal atom moiety is restored to its original al catalyst form. This part of the process may require additional reactions, with Rs or without external reagents, or it may reflect a competition between product and solvent, other ligands, or reactants )ns for coordination sites. Certain minimum criteria must be met in order for ids. these processes to be catalytic. (i) The system is trivial unless there is an appreciable effect on mechanism. The sch usual reaction path may be greatly accelerated by stabilization of the transition state or destabilization of a reactant, or an unusual reaction path may substituent, and be followed because of ext...

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The Reactions of Coordinated Ligands

Cited by 30 publications

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An I²O¹ Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

An I²O¹ Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

First Considerations: Principles, Classification, and History

Metal Ion Control of Chemical Reactions

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The Reactions of Coordinated Ligands

Cited by 30 publications

References 0 publications

An I2O1 Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

An I2O1 Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

First Considerations: Principles, Classification, and History

Metal Ion Control of Chemical Reactions

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An I²O¹ Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation

An I²O¹ Barium Framework Derived from an In‐Situ Metal‐Assisted Ligand Transformation