Dimetal Complexes of a Bibrachial 2+2 Thiolate-based Macrocycle

Anders Lennartson, Vickie McKee, Jane Nelson, Michael Arthurs, Christine Joy McKenzie

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of each of the tren head groups is pendant were isolated in attempts to make the crypts. The Mn(II)2 complex can be used in transmetallation reactions and these probably occur in a stepwise fashion for the heavier, softer metal ions since the plausible intermediates Mn(II)M(II), M = Cd, Pd, were identified. There is evidence for the formation of [2+3] cryptand systems using templating Ag(I) and Cd(II); however, reaction conditions need to be strictly controlled to ensure isolation of either the [2+3] cryptand or the [2+2] macrocyclic complex since ensuing reactions leading to intractable oligomers are competing. The template and transmetallation experiments described here emphasise the relatively greater hydrolytic sensitivity of the thiophenol-derived imino macrocycles and crypts than their better-known phenol-based counterparts.
OriginalsprogEngelsk
TidsskriftSupramolecular Chemistry
Vol/bind24
Sider (fra-til)604-617
Antal sider14
ISSN1061-0278
DOI
StatusUdgivet - 2012

Fingeraftryk

Crown Ethers
Phenol
Oligomers
Metal ions
Experiments
cryptand
thiophenol

Citer dette

Lennartson, Anders ; McKee, Vickie ; Nelson, Jane ; Arthurs, Michael ; McKenzie, Christine Joy. / Dimetal Complexes of a Bibrachial 2+2 Thiolate-based Macrocycle. I: Supramolecular Chemistry. 2012 ; Bind 24. s. 604-617.
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abstract = "Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of each of the tren head groups is pendant were isolated in attempts to make the crypts. The Mn(II)2 complex can be used in transmetallation reactions and these probably occur in a stepwise fashion for the heavier, softer metal ions since the plausible intermediates Mn(II)M(II), M = Cd, Pd, were identified. There is evidence for the formation of [2+3] cryptand systems using templating Ag(I) and Cd(II); however, reaction conditions need to be strictly controlled to ensure isolation of either the [2+3] cryptand or the [2+2] macrocyclic complex since ensuing reactions leading to intractable oligomers are competing. The template and transmetallation experiments described here emphasise the relatively greater hydrolytic sensitivity of the thiophenol-derived imino macrocycles and crypts than their better-known phenol-based counterparts.",
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Dimetal Complexes of a Bibrachial 2+2 Thiolate-based Macrocycle. / Lennartson, Anders ; McKee, Vickie; Nelson, Jane; Arthurs, Michael ; McKenzie, Christine Joy.

I: Supramolecular Chemistry, Bind 24, 2012, s. 604-617.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

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AU - Lennartson, Anders

AU - McKee, Vickie

AU - Nelson, Jane

AU - Arthurs, Michael

AU - McKenzie, Christine Joy

PY - 2012

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N2 - Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of each of the tren head groups is pendant were isolated in attempts to make the crypts. The Mn(II)2 complex can be used in transmetallation reactions and these probably occur in a stepwise fashion for the heavier, softer metal ions since the plausible intermediates Mn(II)M(II), M = Cd, Pd, were identified. There is evidence for the formation of [2+3] cryptand systems using templating Ag(I) and Cd(II); however, reaction conditions need to be strictly controlled to ensure isolation of either the [2+3] cryptand or the [2+2] macrocyclic complex since ensuing reactions leading to intractable oligomers are competing. The template and transmetallation experiments described here emphasise the relatively greater hydrolytic sensitivity of the thiophenol-derived imino macrocycles and crypts than their better-known phenol-based counterparts.

AB - Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of each of the tren head groups is pendant were isolated in attempts to make the crypts. The Mn(II)2 complex can be used in transmetallation reactions and these probably occur in a stepwise fashion for the heavier, softer metal ions since the plausible intermediates Mn(II)M(II), M = Cd, Pd, were identified. There is evidence for the formation of [2+3] cryptand systems using templating Ag(I) and Cd(II); however, reaction conditions need to be strictly controlled to ensure isolation of either the [2+3] cryptand or the [2+2] macrocyclic complex since ensuing reactions leading to intractable oligomers are competing. The template and transmetallation experiments described here emphasise the relatively greater hydrolytic sensitivity of the thiophenol-derived imino macrocycles and crypts than their better-known phenol-based counterparts.

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