Novel Synthesis of Macrocyclic Amine-Thiophenolate Ligands: X-ray Crystal Structure of a Ni4 Complex of an N8S4 Ligand

Kersting, Berthold; Steinfeld, Gunther; Fritz, T.A.; Hausmann, J. Niklas

doi:10.1002/(sici)1099-0682(199912)1999:12<2167::aid-ejic2167>3.0.co;2-f

Cited by 22 publications

(16 citation statements)

References 23 publications

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“…For the bulkier ethyl and propyl derivatives a reaction sequence similar to that used for the alkylation of triazacyclononane13 and cyclam14 was used. The syntheses began with the acylation of known amine 1 ,15 with the anhydrides 2 (Scheme ). The resulting amides 3 were then reduced with lithium aluminium hydride in refluxing THF solution to give the corresponding amines 4 .…”

Section: Resultsmentioning

confidence: 99%

Preparation and Characterization of Co^II, Ni^II, and Zn^II Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

et al. 2005

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N‐Alkylated variants of a Robson‐type 24‐membered hexaazamacrocyclic dinucleating dithiophenolate ligand bearing ethyl and propyl groups have been prepared and their ligating properties towards the 3d elements Ni, Co and Zn have been examined. The new ligands support the formation of dinuclear complexes of the type [(LR)MII2(L')]+, i.e. [(LEt)Ni2(Cl)]+ (7), [(LPr)Ni2(Cl)]+ (8), [(LEt)Ni2(OAc)]+ (9), [(LPr)Ni2(OAc)]+ (10), [(LEt)Ni2(O2COMe)]+ (11), [(LEt)Ni2(O2COEt)]+ (12), [(LEt)Zn2(OAc)]+ (14), [(LEt)Co2(Cl)]+ (17), and [(LEt)Co2(OAc)]+ (18), the overall structures of which are very similar to the corresponding complexes of the parent permethylated ligand system. The use of the longer alkyl chains expands the binding pocket of the complexes to a more conical, “calixarene”‐like cavity and has allowed for the isolation of the trication [(HLEt)Ni2]3+ (13), which is an intermediate in the substitution reactions of 7. Complex 13 reveals a new coordination mode of the supporting ligand with adjacent four‐ and five‐coordinate nickel atoms. Its higher stability is presumably a consequence of the increased steric crowding imposed by the longer alkyl chains of (LEt)2–. These results have thus demonstrated that these highly functionalized ligand systems allow for the stabilization of reactive intermediates. This information can now be used as a guide to further modulate the chemical reactivity of these compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Resultsmentioning

confidence: 99%

Preparation and Characterization of Co^II, Ni^II, and Zn^II Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

et al. 2005

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“…Compound 1 was prepared according to a modified literature procedure [12]. All syntheses were carried out under a protective atmosphere of argon.…”

Section: Methodsmentioning

confidence: 99%

“…Earlier attempts to obtain a [2+1] product from the condensation of 1 with either ethylenediamine or propylenediamine had failed and only [4+2] products had been obtained [12,13]. Despite these findings the condensation of 1 with diethylenetriamine under medium-dilution conditions was carried out and afforded, after subsequent sodium borohydride reduction of the tetraimine-dithioether intermediate, a single compound L1 in 95% yield.…”

Section: Ig a N D Syn Th Esesmentioning

confidence: 99%

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Synthesis and Coordination Chemistry of Novel Binucleating Macrocyclic Ligands with Amine-thioether and Amine-thiophenolate Donor Functions

Klingele

Steinfeld

Kersting

2001

Zeitschrift Für Naturforschung B

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The ability of the aromatic tetraaldehyde l,2-bis(4-rm-butyl-2,6-diformylphenylsulfanyl)ethane (1 ) to function as a precursor in the preparation of binucleating hexaamine-dithiolate lig ands has been investigated. Reductive amination of compound 1 with bis(aminoethyl)amine un der medium-dilution conditions affords the macrobicyclic hexaamine-dithioether compound L 1. Deprotection of the [1+2] condensation product gives the corresponding 24-membered hexaamine-dithiophenol ligand H2L2. The formulation of L 1 as a macrobicyclic amine-thioether was confirmed by an X-ray crystal structure determination of the tetranuclear nickel(II) complex of L 1, [{ (L jN iiC lili^-C l^K B P h ;) (2b). The formulation of the doubly deprotonated form (L2)2-of H2L2 as a 24-membered amine-thiophenolate ligand was confirmed by an X-ray crystal structure determination of the dinuclear cobalt(III) complex, [(L2)Com(^-OH)](C1 0 4 ) 2 • Cl (3). The preparation and the crystal structures of the new compounds are described.

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“…Scheme 1.2 illustrates the general procedure. Reductive amination of tetraaldehyde 1 [39] with diethylene triamine under medium-dilution conditions affords the macrobicyclic hexaaza-dithioether 2 in excellent yields (>90%) [40]. The aliphatic thioether linkage serves both as a protecting group for the air-sensitive thiophenolate groups and as a template function.…”

Section: Synthesismentioning

confidence: 99%

Chemistry of metalated container molecules

Kersting¹,

Lehmann²

2009

Advances in Inorganic Chemistry

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Novel Synthesis of Macrocyclic Amine-Thiophenolate Ligands: X-ray Crystal Structure of a Ni4 Complex of an N8S4 Ligand

Cited by 22 publications

References 23 publications

Preparation and Characterization of Co^II, Ni^II, and Zn^II Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

Preparation and Characterization of Co^II, Ni^II, and Zn^II Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

Synthesis and Coordination Chemistry of Novel Binucleating Macrocyclic Ligands with Amine-thioether and Amine-thiophenolate Donor Functions

Chemistry of metalated container molecules

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Novel Synthesis of Macrocyclic Amine-Thiophenolate Ligands: X-ray Crystal Structure of a Ni4 Complex of an N8S4 Ligand

Cited by 22 publications

References 23 publications

Preparation and Characterization of CoII, NiII, and ZnII Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

Preparation and Characterization of CoII, NiII, and ZnII Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

Synthesis and Coordination Chemistry of Novel Binucleating Macrocyclic Ligands with Amine-thioether and Amine-thiophenolate Donor Functions

Chemistry of metalated container molecules

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Preparation and Characterization of Co^II, Ni^II, and Zn^II Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates

Preparation and Characterization of Co^II, Ni^II, and Zn^II Complexes of Sterically Demanding Hexaazamacrocyclic Dithiophenolates