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Gas-phase structures of 1-adamantylphosphines, PH n (1-Ad)3−n (n = 1–3)

Abstract

The gas-phase structure of 1-adamantylphosphine has been determined by electron diffraction, supplemented with data from ab initio and DFT calculations. The adamantyl fragment was modeled with local C 3v symmetry and the phosphino group was found to be in a position almost bisecting a mirror plane of the adamantyl group, giving the molecule overall approximate C s symmetry. There is a small displacement of the C–P bond from the local threefold axis of the adamantyl group. Geometry optimizations were also performed for bis-(1-adamantyl)phosphine (C 1 point-group symmetry) and tris-(1-adamantyl)phosphine (C 3 symmetry), demonstrating extremely crowded environments around the phosphorus atoms leading to adamantyl groups that were much less symmetric. The adamantyl groups were also found to twist by a significant amount to minimize the strain.

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Acknowledgments

We thank the UK EPSRC for funding the GED research (grant GR/K44411) and the NSCCS [12] and EaStCHEM RCF [13] for computational resources. The RCF is partially funded through the eDIKT2 initiative.

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Correspondence to Derek A. Wann.

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Wann, D.A., Turner, A.R., Goerlich, J.R. et al. Gas-phase structures of 1-adamantylphosphines, PH n (1-Ad)3−n (n = 1–3). Struct Chem 22, 263–267 (2011). https://doi.org/10.1007/s11224-010-9695-6

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Keywords

  • 1-Adamantylphosphines
  • Gas electron diffraction
  • Quantum chemical calculations
  • Molecular structure