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Thiophene-linked azacryptand sites for dicopper and disilver; Thiophene sulfur as an inert spacer?

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UNSPECIFIED (1996) Thiophene-linked azacryptand sites for dicopper and disilver; Thiophene sulfur as an inert spacer? JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (14). pp. 3021-3030. ISSN 0300-9246

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Abstract

Two disilver cryptates of the thiophene-spaced azacryptand hexa Schiff bases N[(CH2)(n)N=CHRHC=N(CH2)(n)]N-3 (n = 2 or 3, R = thiophene-2,5-diyl) and with the dicopper(I) cryptate where n? = 2 have been structurally characterised. The dinuclear separation increases by 0.36 Angstrom on going from the disilver complex of the n = 2 cryptand, to the n = 3 analogue, with that in the dicopper(I) cryptate intermediate, but little difference in cryptand conformation is observed in the three complexes. Proton NMR spectra show three-bond (H-C=N-Ag) coupling of each imino CH proton to Ag-109,Ag-107, confirmed by an Ag-109 insensitive nuclei enhanced by polarisation transfer experiment. No copper(II) cryptates were obtained with the hexa(Schiff-base) cryptands. The analogous octaamino compounds, generate dicopper(II) cryptates which accommodate bridging anions in cascade fashion, with a bridging disposition collinear, Cu-NNN-Cu, in the mu-azido-, but non-linear, Cu-O(H)-Cu, in the mu-hydroxo-cryptate. Both the hexa(Schiff-base) and octaamino cryptates are very similar to inert-spacer azacryptates and give no evidence for hemico-ordination of thiophene sulfur.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Journal or Publication Title: JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Publisher: ROYAL SOC CHEMISTRY
ISSN: 0300-9246
Date: 21 July 1996
Number: 14
Number of Pages: 10
Page Range: pp. 3021-3030
Publication Status: Published
URI: http://wrap.warwick.ac.uk/id/eprint/18546

Data sourced from Thomson Reuters' Web of Knowledge

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