Chiral Scrambling and Independent Crystallization of <scp>d</scp>4, <scp>l</scp>4, and <scp>d</scp>2<scp>l</scp>2 Isomers of an AuI4CoIII2 Hexanuclear Complex with Mixed Penicillaminate and Bis(diphenylphosphino)ethane

Yoshinari, Nobuto; Li, Chan; Lee, Raeeun; Kuwamura, Naoto; Igashira‐Kamiyama, Asako; Konno, Takumi

doi:10.1021/acs.inorgchem.5b01549

Cited by 12 publications

(3 citation statements)

References 41 publications

(17 reference statements)

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“…These compounds function as a multidentate metalloligand by using thiolato, amine, and carboxy groups, constructing a variety of multinuclear and metallosupramolecular structures . For example, we found that [Au 2 (dppe)( d ‐Hpen) 2 ] (dppe=1,2‐bis(diphenylphosphino)ethane) reacts with Co 2+ under aerobic conditions to form a discrete Au I 4 Co III 2 hexanuclear structure of [Au 2 Co 2 (dppe) 2 ( d ‐pen) 4 ] 2+ , in which the two [Au 2 (dppe)( d ‐pen) 2 ] 2− metalloligands bridge two Co III ions in a skewed cyclic form . To expand this metalloligand system, we thought it worthwhile to design ring‐type metalloligands, in which [Au 2 (L)] 2+ units are linked through thiolato groups of d ‐pen, leaving free amine and carboxylate groups that act as coordination arms to other metal centers.…”

Section: Methodsmentioning

confidence: 99%

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

Nishiura

Kojima

Igashira‐Kamiyama

et al. 2018

Chemistry An Asian Journal

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A unique example of a ring-to-cage structural conversion in a multinuclear gold(I) coordination system with d-penicillamine (d-H pen) is reported. The reaction of [Au Cl (dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) with d-H pen in a 1:1 ratio gave [Au (dppe) (d-pen) ] ([1]), in which two [Au (dppe)] units are linked by two d-pen S atoms in a cyclic form so as to have two bidentate-N,O coordination arms. The subsequent reaction of [1] with Cu(OTf) afforded [Au Cu(dppe) (d-pen) ] ([2] ), in which a Cu ion is chelated by the two coordination arms in [1] to form an Au Cu bicyclic metallocage. A similar reaction using Cu(NO ) was accompanied by the ring expansion of [1] to [Au (dppe) (d-pen) ], leading to the production of [Au Cu (dppe) (d-pen) ] ([3] ). In [3] , two Cu ions are each chelated by the two coordination arms to form an Au Cu tricyclic metallocage, accommodating a nitrate ion. The use of Ni(NO ) or Ni(OAc) instead of Cu(NO ) commonly gave a tricyclic metallocage of [Au Ni (dppe) (d-pen) ] ([4] ), but a water molecule was accommodated inside the Au Ni metallocage.

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Section: Methodsmentioning

confidence: 99%

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

Nishiura

Kojima

Igashira‐Kamiyama

et al. 2018

Chemistry An Asian Journal

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“…In addition, it is also possible for the d ‐pen ligands to be chemically modified to control the coordination behavior of the [Au( d ‐pen‐ S )] – coordination arms. Efforts in this direction have already begun and involve an N ‐substituted d ‐penicillamine 56 or an l ‐configurational penicillamine 57. It is expected that additional novel compounds, such as NCIS, will be discovered during the course of our upcoming studies.…”

Section: Summary and Future Outlookmentioning

confidence: 99%

Metallosupramolecular Structures Derived from a Series of Diphosphine-bridged Digold(I) Metalloligands with Terminald-Penicillamine

Yoshinari

Konno

2016

The Chemical Record

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In this report, we describe our recent work on the development of a new family of chiral heteroleptic digold(I) metalloligands with mixed diphosphine and d-penicillaminate (d-pen), [Au2 (dppx)(d-pen-S)2 ](2-) (dppx = PPh2 (CH2 )n PPh2 , n = 1-5) and their application for the construction of chiral multinuclear and metallosupramolecular structures. The reactions of the metalloligands with 3d metal ions produce a variety of chiral heterobimetallic structures retaining the digold(I) metalloligand structure, ranging from discrete trinuclear to infinite helix structures that depend on the type of dppx. In addition, monophosphine and triphosphine analogues of the metalloligands were designed, and their coordination behavior is discussed to show the essential properties and potential extensibility of this class of metalloligands.

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“…Recently, we have developed a new class of digold(I) metalloligands, [Au I 2 (dppx)(D-pen) 2 ] 2− (dppx = PPh 2 [CH 2 ] n PPh 2 , n = 1-5; D-pen = D-penicillaminate), [20][21][22][23][24][25][26][27][28][29] as part of our continuing study on the rational construction of multinuclear and metallosupramolecular coordination compounds based on the metalloligand approach. [30][31][32] Since this class of digold(I) metalloligands possesses hydrophobic phenyl groups as well as hydrophilic amine and carboxyl groups, it is expected that the resulting metal complexes can form an unusual arrangement of ionic species via hydrogen-bonding and π interactions in the solid state.…”

Section: Introductionmentioning

confidence: 99%

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

Pratikha

Inoue

Arai

et al. 2020

J Chinese Chemical Soc

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The reaction of Na[Co III (D-ebp)] (D-H 4 ebp = N,N 0-ethylenebis[D-penicillamine]) with [(Au I Cl) 2 (dppe)] (dppe = 1,2-bis[diphenylphosphino]ethane) gave a cationic Au I 4 Co III 2 hexanuclear complex, [Co III 2 (L Au4)] 2+ ([1] 2+), where [L Au4 ] 4− is a cyclic tetragold(I) metalloligand with a 32-membered ring, [Au I 4 (dppe) 2 (D-ebp) 2 ] 4−. Complex [1] 2+ crystallized with NO 3 − to produce a charge-separation (CS)-type ionic solid of [1](NO 3) 2. In [1](NO 3) 2 , the complex cations are assembled to form cationic supramolecular hexamers of {[1] 2+ } 6 , which are closely packed in a face-centered cubic (fcc) lattice structure. The nitrate anions of [1](NO 3) 2 were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO 3 − } 4 and {NO 3 − } 6 , respectively. An analogous CS-type ionic solid formulated as [Ni II Co III (L Au4)](NO 3) ([2](NO 3)) was obtained when a 1:1 mixture of Na[Co III (D-ebp)] and [Ni II (D-H 2 ebp)] was reacted with [(Au I Cl) 2 (dppe)], accompanied by the conversion of the diamagnetic, squareplanar [Ni II (D-H 2 ebp)] to the paramagnetic, octahedral [Ni II (D-ebp)] 2−. While the overall fcc structure in [2](NO 3) was similar to that of [1](NO 3) 2 , none of the nitrate anions were accommodated in any hydrophobic tetrahedral interstice, reflecting the difference in the complex charges between [1] 2+ and [2] + .

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Chiral Scrambling and Independent Crystallization of d₄, l₄, and d₂l₂ Isomers of an Au^I₄Co^III₂ Hexanuclear Complex with Mixed Penicillaminate and Bis(diphenylphosphino)ethane

Cited by 12 publications

References 41 publications

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

Metallosupramolecular Structures Derived from a Series of Diphosphine-bridged Digold(I) Metalloligands with Terminald-Penicillamine

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

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Chiral Scrambling and Independent Crystallization of d4, l4, and d2l2 Isomers of an AuI4CoIII2 Hexanuclear Complex with Mixed Penicillaminate and Bis(diphenylphosphino)ethane

Cited by 12 publications

References 41 publications

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

Metallosupramolecular Structures Derived from a Series of Diphosphine-bridged Digold(I) Metalloligands with Terminald-Penicillamine

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

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Chiral Scrambling and Independent Crystallization of d₄, l₄, and d₂l₂ Isomers of an Au^I₄Co^III₂ Hexanuclear Complex with Mixed Penicillaminate and Bis(diphenylphosphino)ethane