Syntheses and Structures of Digold Complexes of Macrobicyclic Dibridgehead Diphosphines That Can Turn Themselves Inside Out
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When isomers of the dibridgehead diphosphine P((CH 2) 14) 3P (2) are treated with Me 2SAuCl, 2•(AuCl) 2 is obtained in high yields. With in,in-/out,out-2 (97:3 equilibrium mixture), only a single isomer can be detected by low-temperature NMR, which is assigned as out,out-2•(AuCl) 2 on the basis of the crystal structure. With in,out-2, in,out-2•(AuCl) 2 is obtained, as confirmed by a crystal structure. Both lattices show hydrogen bonding between the AuCl moieties of one molecule and the PCH 2 hydrogen atoms of a neighboring molecule. This requires access to the backside of the P-Au-Cl linkages, distorting the diphosphine cages. When out,out-2•(AuCl) 2 is treated with CH 3Li, out,out-2•(AuCH 3) 2 can be isolated (91%). Analogous hydrogen bonding is impossible, and this molecule crystallizes with a much more symmetrical cage, the center of which is occupied by a methylcyclopentane solvate. © 2011 American Chemical Society.
author list (cited authors)
Stollenz, M., Bhuvanesh, N., Reibenspies, J. H., & Gladysz, J. A.