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Syntheses and Structures of Digold Complexes of Macrobicyclic Dibridgehead Diphosphines That Can Turn Themselves Inside Out

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ORGANOMETALLICS
卷 30, 期 24, 页码 6510-6513

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AMER CHEMICAL SOC
DOI: 10.1021/om200924g

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  1. National Science Foundation [CHE-0719267]

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When isomers of the dibridgehead diphosphine P((CH2)(14))(3)P (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,out2-(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,out2.(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.

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