Please use this identifier to cite or link to this item:;2-T
Title: Self-assembly of gold(I) rings and reversible formation of organometallic [2]catenanes
Authors: McArdle, C.P.
Irwin, M.J.
Jennings, M.C.
Vittal, J.J. 
Puddephatt, R.J.
Keywords: Aurophilicity
Molecular recognition
Issue Date: 2-Feb-2002
Source: McArdle, C.P.,Irwin, M.J.,Jennings, M.C.,Vittal, J.J.,Puddephatt, R.J. (2002-02-02). Self-assembly of gold(I) rings and reversible formation of organometallic [2]catenanes. Chemistry - A European Journal 8 (3) : 723-734. ScholarBank@NUS Repository.;2-T
Abstract: The reaction of the digold(I) diacetylide [(AuCCCH2OC6H4)2CMe2] with diphosphane ligands can lead to formation of either macrocyclic ring complexes or [2]catenanes by self-assembly. This gives an easy route to rare organometallic [2]catenanes, and the effect of the diphosphane ligand on the selectivity of self-assembly is studied. With diphosphane ligands Ph2P(CH2)xPPh2, the simple ring complex [Au2{(CCCH2OC6H4)2CMe 2}(Ph2P(CH2)xPPh2)] is formed selectively when x = 2, but the [2]catenanes [Au2{(CCCH2OC6H4)2CMe 2}(Ph2P(CH2)xPPh2)] 2 are formed when x = 4 or 5. When x = 3, a mixture of the simple ring and [2]catenane is formed, along with the "double-ring" complex, [Au4{(CCCH2OC6H4)2CMe 2}2(Ph2P(CH2)3PPh 2)2] and a "hexamer" [{Au2[(CCCH2OC6H4)2 CMe2](Ph2P(CH2)3PPh 2)}6] whose structure is not determined. A study of the equilibria between these complexes by solution NMR techniques gives insight into the energetics and mechanism of [2]catenane formation. When the oligomer [(AuCCCH2OC6H4)2CMe2] was treated with a mixture of two diphosphane ligands, or when two [2]catenane complexes [{Au2[(CCCH2OC6H4) 2CMe2](diphosphane)}2] were allowed to equilibrate, only the symmetrical [2]catenanes were formed. The diphosphanes Ph2PCCPPh2, trans-[Ph2PCH=CHPPh2] and (Ph2PC5H4)2Fe give the corresponding ring complexes [Au2{(CCCH2OC6H4)2 CMe2}(diphosphane)], and the chiral, unsymmetrical diacetylide [Au2{ (CCCH2OC6H4C(Me) (CH2CMe2)C6H3OCH2CC)] gives macrocyclic ring complexes with all diphosphane ligands Ph2P(CH2)xPPh2 (x = 2-5).
Source Title: Chemistry - A European Journal
ISSN: 09476539
DOI: 10.1002/1521-3765(20020201)8:33.0.CO;2-T
Appears in Collections:Staff Publications

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