Design and sterospecific synthesis of modular ligands based upon cis-1,3-trans-5-substituted cyclohexanes

Fielden, John; Sprott, Joanna; Cronin, Leroy

doi:10.1039/b503606b

Cited by 9 publications

(10 citation statements)

References 30 publications

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“…The ligands cis-3,5-diamino-trans-hydroxycyclohexane (DAHC), cis-3,5-diaminotrans-methoxycyclohexane (DAMC), and glutaric acid bis-(cis-3,5diaminocyclohexyl) ester (GADACE) were synthesized starting from cis-1,3,5-cyclohexanetriol. 30 All other reagents and solvents were bought commercially as AR grade (Aldrich/Lancaster) and used without further purification. Complexations were performed in the ambient atmosphere, using between 0.52 and 0.7 mol of copper(II) salt/mol of ligand chelating group.…”

Section: Methodsmentioning

confidence: 99%

“…Materials, Methods, and Instrumentation. The ligands cis -3,5-diamino- trans -hydroxycyclohexane (DAHC), cis -3,5-diamino- trans -methoxycyclohexane (DAMC), and glutaric acid bis-( cis -3,5-diaminocyclohexyl) ester (GADACE) were synthesized starting from cis -1,3,5-cyclohexanetriol . All other reagents and solvents were bought commercially as AR grade (Aldrich/Lancaster) and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

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Controlling Aggregation of Copper(II)-Based Coordination Compounds: From Mononuclear to Dinuclear, Tetranuclear, and Polymeric Copper Complexes

et al. 2006

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The use of a strategy combining ligand design and changes of reaction conditions has been investigated with the goal of directing the assembly of mononuclear, dinuclear, tetranuclear, and polymeric copper(II) complexes. As a result, closely related copper monomers, alkoxo dimers, and hydroxo cubanes, along with a carbonate-bridged polymeric species, have been synthesized using the rigid, aliphatic amino ligands cis-3,5-diamino-trans-hydroxycyclohexane (DAHC), cis-3,5-diamino-trans-methoxycyclohexane (DAMC), and the glutaryl-linked derivative glutaric acid bis-(cis-3,5-diaminocyclohexyl) ester (GADACE). The composition of the monomeric complex has been determined by X-ray crystallography as [Cu(DAHC)2](ClO4)2 (1), the two dimers as [{Cu(DAHC)(OMe)}2](ClO4)2.MeOH (2) and [{Cu(DAMC)(OMe)(ClO4)}2] (3), the three Cu4O4 cubanes as [{Cu(DAHC)(OH)}4](ClO4)(4).2.5MeOH (4), [{Cu(DAMC)(OH)}4](ClO4)4.H2O (5), and [{Cu2(OH)2(GADACE)}2]Cl4.2MeOH.6H2O (6), and an infinite-chain structure as [{Cu(DAHC)(CO3)}n] (7). Furthermore, the cubane structures 4 and 5 have been investigated magnetically. Our studies indicate that formation of the monomeric, dimeric, and tetranuclear DAHC and DAMC complexes can be controlled by small changes in reaction conditions and that further preorganization of the ligand moiety by linking the DAHC cores (GADACE) allows more effective direction of the self-assembly of the Cu4O4 cubane core.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Controlling Aggregation of Copper(II)-Based Coordination Compounds: From Mononuclear to Dinuclear, Tetranuclear, and Polymeric Copper Complexes

et al. 2006

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“…[16] All other reagents and solvents were purchased (Fisher/Lancaster/Riedel-de Haën/Aldrich) as AR grade and used without further purification. Deuterated solvents were obtained from Aldrich.…”

Section: Methodsmentioning

confidence: 99%

“…[11] Recent work in our laboratory has focused on the synthesis and coordination behaviour of the small, cyclohexanebased aliphatic amino ligands r-1,t-3,t-5-triaminocyclohexane (TACH) [12][13][14] and t-3,t-5-diamino-r-1-hydroxycyclohexane (DAHC). [15][16][17] While becoming rigid upon coordination due to conformational locking of the cyclohexane 3930 coordinate dinuclear mesocate structures [{Ag(DDOP)} 2 ]-(CF 3 SO 3 ) 2 (3) and [{Ag(DDMOP)} 2 ](CF 3 SO 3 ) 2 ·0.5MeOH (4). It is thought that the mononuclear, octahedral complexes in the case of zinc(II) and cadmium(II) result from the energetic stabilisation gained through two extra coordinate bonds, while in the case of silver(I) the lower propensity of the metal centre for six-coordination causes the ligand to retain its energetically preferred dinucleating conformation and to form the mesocates.…”

Section: Introductionmentioning

confidence: 99%

Metal‐Dependent Formation of Mononuclear Complexes and M₂L₂ Mesocates with Schiff‐Base Ligands

et al. 2006

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“…The ligands DAMC and DATC were synthesized starting from cis-1,3,5-cyclohexanetriol. 27 All other reagents and solvents were purchased as AR grade and used without further purification. Deuterated solvents were obtained from Aldrich.…”

Section: Methodsmentioning

confidence: 99%

Ligand and Counterion Control of Ag(I) Architectures: Assembly of a {Ag₈} Ring Cluster Mediated by Hydrophobic and Ag···Ag Interactions

et al. 2007

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A strategy combining ligand design and counterion variation has been used to investigate the assembly of silver(I) complexes. As a result, dinuclear, octanuclear, and polymeric silver(I) species have been synthesized by complexation of the rigid aliphatic amino ligands cis-3,5-diamino-trans-hydroxycyclohexane (DAHC), cis-3,5-diamino-trans-methoxycyclohexane (DAMC), and cis-3,5-diamino-trans-tert-butyldimethylsilylanyloxycyclohexane (DATC) with silver(I) triflate, nitrate, and perchlorate. The compositions of these aggregates, established by X-ray crystallography and elemental analysis, are [{Ag(DAHC)}2](CF3SO3)2 (1), [{Ag(DAMC)}2](CF3SO3)2 (2), [{Ag(DAMC)}2](NO3)2 (3), [{Ag(DATC)}6{Ag(DAHC)}2](NO3)8 (4), and [{Ag(DATC}n](NO3)n (5), where the DAHC present in 4 is formed by in situ hydrolysis of the acid labile silyl ether group. The type of aggregate formed depends both upon the noncoordinating O-substituent of the ligand and the (also noncoordinating) counterion, with the normal preference of the ligand topology for forming Ag2L2 structures being broken by introduction of the bulky, lipophilic O-tert-butyldimethylsilyl (TBDMS) group. Of particular note is the octanuclear silver ring structure 4, which is isolated only when both the O-TBDMS group and the nitrate counteranion are present and is formed from four Ag2L2 dimers connected by Ag...Ag and hydrogen-bonding interactions. Diffusion rate measurement of this {Ag8} complex by 1H NMR (DOSY) indicates dissociation in CD3OD and CD3CN, showing that this supramolecular ring structure is formed upon crystallization, and establishing a qualitative limit to the strength of Ag...Ag interactions in solution. When solutions of the {Ag8} cluster in methanol are kept for several days though, a new UV-vis absorption is observed at around 430 nm, consistent with the formation of silver nanoparticles.

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Design and sterospecific synthesis of modular ligands based upon cis-1,3-trans-5-substituted cyclohexanes

Cited by 9 publications

References 30 publications

Controlling Aggregation of Copper(II)-Based Coordination Compounds: From Mononuclear to Dinuclear, Tetranuclear, and Polymeric Copper Complexes

Controlling Aggregation of Copper(II)-Based Coordination Compounds: From Mononuclear to Dinuclear, Tetranuclear, and Polymeric Copper Complexes

Metal‐Dependent Formation of Mononuclear Complexes and M₂L₂ Mesocates with Schiff‐Base Ligands

Ligand and Counterion Control of Ag(I) Architectures: Assembly of a {Ag₈} Ring Cluster Mediated by Hydrophobic and Ag···Ag Interactions

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Design and sterospecific synthesis of modular ligands based upon cis-1,3-trans-5-substituted cyclohexanes

Cited by 9 publications

References 30 publications

Controlling Aggregation of Copper(II)-Based Coordination Compounds: From Mononuclear to Dinuclear, Tetranuclear, and Polymeric Copper Complexes

Controlling Aggregation of Copper(II)-Based Coordination Compounds: From Mononuclear to Dinuclear, Tetranuclear, and Polymeric Copper Complexes

Metal‐Dependent Formation of Mononuclear Complexes and M2L2 Mesocates with Schiff‐Base Ligands

Ligand and Counterion Control of Ag(I) Architectures: Assembly of a {Ag8} Ring Cluster Mediated by Hydrophobic and Ag···Ag Interactions

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Product

Resources

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Metal‐Dependent Formation of Mononuclear Complexes and M₂L₂ Mesocates with Schiff‐Base Ligands

Ligand and Counterion Control of Ag(I) Architectures: Assembly of a {Ag₈} Ring Cluster Mediated by Hydrophobic and Ag···Ag Interactions