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


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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  1. 1.

    Brook AG, Abdesaken F, Gutekunst B, Gutekunst G, Kallury RK (1981) J Chem Soc Chem Commun 191:1981

    Google Scholar 

  2. 2.

    Shepherd BD, Powell DR, West R (1989) Organometallics 8:2664

    Article  CAS  Google Scholar 

  3. 3.

    Goerlich JR, Weiss J-V, Jones PG, Schmutzler R (1992) Phosphorus Sulfur Silicon 66:223

    Article  CAS  Google Scholar 

  4. 4.

    Goerlich JR, Schmutzler R (1995) Phosphorus Sulfur Silicon 101:245

    Article  CAS  Google Scholar 

  5. 5.

    Goerlich JR, Schmutzler R (1995) Phosphorus Sulfur Silicon 101:245

    Article  CAS  Google Scholar 

  6. 6.

    Patsanovskii II, Yarkova EG, Shakirov IK, Gulyaeva ZR, Ishmaeva EA, Muller S, Schmutzler R (1995) Zh Org Khim 21:1580

    Google Scholar 

  7. 7.

    Stetter H, Last WD (1969) Chem Ber 102:3364

  8. 8.

    Huntley CM, Laurenson GS, Rankin DWH (1980) J Chem Soc Dalton Trans 954

  9. 9.

    Lewis JR, Brain PT, Rankin DWH (1997) Spectrum 15:7

    Google Scholar 

  10. 10.

    Hinchley SL, Robertson HE, Borisenko KB, Turner AR, Johnston BF, Rankin DWH, Ahmadian M, Jones JN, Cowley AH (2004) Dalton Trans 2469

  11. 11.

    Ross AW, Fink M, Hilderbrandt R (1992) In Wilson AJC (ed) International tables for crystallography, vol C. Kluwer Academic Publishers, Dordrecht, Netherlands, pp 245

  12. 12.

    National Service for Computational Chemistry Software (NSCCS). URL

  13. 13.

    EaStCHEM Research Computing Facility ( This facility is partially supported by the eDIKT initiative (

  14. 14.

    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB,. Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) GAUSSIAN 03 (Revision D.01). Gaussian, Inc., Wallingford, CT

  15. 15.

    Blake AJ, Brain PT, McNab H, Miller J, Morrison CA, Parsons S, Rankin DWH, Robertson HE, Smart BA (1996) J Phys Chem 100:12280

    Article  CAS  Google Scholar 

  16. 16.

    Brain PT, Morrison CA, Parsons S, Rankin DWH (1996) J Chem Soc Dalton Trans 4589

  17. 17.

    Mitzel NW, Rankin DWH (2003) Dalton Trans 3650

  18. 18.

    Sipachev VA (1985) J Mol Struct 121:143

    Google Scholar 

  19. 19.

    Sipachev VA (2001) J Mol Struct 567:67

    Article  Google Scholar 

  20. 20.

    Oberhammer H, Schmutzler R, Stelzer O (1978) Inorg Chem 17:1254

    Article  CAS  Google Scholar 

  21. 21.

    Hinchley SL, Haddow MF, Rankin DWH (2004) Dalton Trans 384

  22. 22.

    Hinchley SL, Haddow MF, Rankin DWH (2004) Inorg Chem 43:5522

    Article  CAS  Google Scholar 

  23. 23.

    Hinchley SL, Smart BA, Morrison CA, Robertson HE, Rankin DWH, Zink R, Hassler K (1999) J Chem Soc Dalton Trans 2303

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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).

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