Monomer, dimer or cyclic helicate? Coordination diversity with hard–soft P,N-donor ligands

Constable, E. C. and Hostettler, N. and Housecroft, C. E. and Murray, N. and Schönle, J. and Soydaner, U. and Walliser, R. M. and Zampese, J. A.. (2013) Monomer, dimer or cyclic helicate? Coordination diversity with hard–soft P,N-donor ligands. Dalton Transactions, 42 (14). pp. 4970-4977.

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Official URL: http://edoc.unibas.ch/dok/A6165175

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We report the synthesis of copper(I) complexes of three ligands which contain a potential P,N,N,P-metal binding site. Elemental analysis confirms that the bulk products possess a composition of [CuL][PF6] where L = 1, 2 or 3. Electrospray mass spectrometry (ESI MS) provides evidence for speciation in MeCN or MeOH solutions and the formation of both [CuL]+ and [Cu2L2]2+; addition of NaCl to the ESI MS samples aids the observation of dinuclear species as [Cu2L2Cl]+ ions. NMR spectroscopic data for a CD3CN solution of [Cu(1)][PF6] were consistent with a mononuclear species, but more complex multinuclear spectra were observed for the same compound dissolved in CD2Cl2. In the solid state, dimeric species dominate. Crystals grown from CH2Cl2 solutions of [Cu(1)][PF6] are found to be [Cu2(1)2][PF6]2·6CH2Cl2; each Cu+ ion in the centrosymmetric cation is bound in an N,O,P,P-coordination sphere, the N-donor originating from the pyridine ring. In [Cu2(3)2][PF6]2, each bridging ligand in the centrosymmetric [Cu2(3)2]2+ ion acts as a P,N-chelate to each Cu+ ion. Competing with this dimeric assembly is that of a circular helicate in which each ligand 3 bridges adjacent pairs of copper(I) ions in a chiral, hexameric complex; both the Δ,Δ,Δ,Δ,Δ,Δ- and Λ,Λ,Λ,Λ,Λ,Λ-enantiomers are present in the crystal lattice; in [Cu6(3)6]6+, each ligand coordinates as a bis(P,N-chelate). The solution absorption spectra of [Cu(1)][PF6], [Cu(2)][PF6] and [Cu(3)][PF6] are dominated by ligand-based transitions and none of the copper(I) complexes exhibits emissive behaviour in solution.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Hostettler, Niklaus and Murray, Niamh Sarah and Schönle, Jonas and Soydaner, Mehmet Ali Umut and Walliser, Roche Marcel and Zampese, Jennifer Ann
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:03 May 2017 13:53
Deposited On:13 Sep 2013 07:56

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