Syntheses and Structures of Digold Complexes of Macrobicyclic Dibridgehead Diphosphines That Can Turn Themselves Inside Out
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https://figshare.com/articles/dataset/Syntheses_and_Structures_of_Digold_Complexes_of_Macrobicyclic_Dibridgehead_Diphosphines_That_Can_Turn_Themselves_Inside_Out/2568841
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资源简介：
When isomers of the dibridgehead diphosphine P((CH2)14)3P (2) are treated
with Me2SAuCl, 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 PCH2 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 CH3Li, out,out-2·(AuCH3)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.
创建时间：
2016-02-22
