Journal of the Chemical Society, Dalton Transactions p. 479 - 489 (1996)
Update date:2022-08-10
Topics:
Copley, Royston C. B.
Mingos, D. Michael P.
Crystal structure analyses of [Au11(PMePh2)10][C2B 9H12]3·4thf (thf = tetrahydrofuran) and [Au11(PMePh2)10][C2B 9H12]3 showed the metal framework of the [Au11(PMePh2)10]3+ cation to approximate to a centred bicapped square antiprism, with idealized D4d symmetry. Symmetry-related cage distances and angles have similar mean values but different ranges in the two structures, with the latter having greater consistency in the peripheral bond lengths but more distortion in the squares of the antiprism. It is suggested that these differences are directly related to the ligand packing around the metal skeletons. The cations of the two clusters cannot be superimposed in any orientation. It is possible to relate a centred bicapped square antiprism to the previously reported undecagold cage geometry, although they belong to different symmetry point groups. The largest differences between the idealized C3v and D4d frameworks centre around three adjacent peripheral sites. The movements required to interconvert the geometries take place about a common mirror plane and appear to be closely related to those of the diamond-square-diamond rearrangement mechanism. Fluxional interconversions of this type provide a possible explanation for the 31P-{1H} NMR spectra of the Au11 cluster compounds.
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