Selectivity in the Self-Assembly of Organometallic Gold(I) Rings and [2]Catenanes
The selectivity of formation of organometallic rings or [2]catenanes [{X(4-C6H4OCH2C⋮CAu)2(μ-Ph2PZPPh2)} n ], n =1 or 2, respectively, has been studied as a function of the hinge group X and the diphosphine ligand [X = O, S, SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10; Z = (CH2) m with m = 2−5]. When Z = (...
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Published in | Organometallics Vol. 24; no. 21; pp. 5004 - 5014 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
10.10.2005
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Online Access | Get full text |
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Summary: | The selectivity of formation of organometallic rings or [2]catenanes [{X(4-C6H4OCH2C⋮CAu)2(μ-Ph2PZPPh2)} n ], n =1 or 2, respectively, has been studied as a function of the hinge group X and the diphosphine ligand [X = O, S, SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10; Z = (CH2) m with m = 2−5]. When Z = (CH2)3, mixing of pairs of compounds with different C 2 v -symmetrical hinge groups (X, X‘ = SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10) led to formation of an equilibrium mixture containing the unsymmetrical [2]catenanes [{X(4-C6H4OCH2C⋮CAu)2(μ-Ph2PZPPh2)}{X‘(4-C6H4OCH2C⋮CAu)2(μ-Ph2PZPPh2)], as identified by NMR spectroscopy. The complexes with Z = (CH2)4 exist in solution predominantly as the macrocycles and so do not form analogous mixed diacetylide complexes. When the hinge group contained a prochiral carbon center (X = CHMe, CMePh, 1,1-indanylidene), only achiral macrocycles [X(4-C6H4OCH2C⋮CAu)2(μ-Ph2PZPPh2)] were formed in solution when Z = (CH2)4, but mixtures containing both achiral macrocycles and chiral [2]catenane were formed when Z = (CH2)3. In several cases, the solid-state structures of the isolated complexes were not representative of the structures in solution, with macrocycles being dominant in solution and [2]catenanes formed preferentially during crystallization. |
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Bibliography: | ark:/67375/TPS-X1N39PCL-3 istex:C81CA77AE3AF3BCE5689AFB4B8AFE844332B5EA4 |
ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om050588o |