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

D.A. Wann; A.R. Turner; J.R. Goerlich; L.J. Kettle; R. Schmutzler; D.W.H. Rankin

doi:10.1007/s11224-010-9695-6

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

D.A. Wann, A.R. Turner, J.R. Goerlich, L.J. Kettle, R. Schmutzler, D.W.H. Rankin

Chemistry

Research output: Contribution to journal › Article › peer-review

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. © 2010 Springer Science+Business Media, LLC.

Original language	English
Pages (from-to)	263-267
Journal	Structural Chemistry
Volume	22
Issue number	2
DOIs	https://doi.org/10.1007/s11224-010-9695-6
Publication status	Published - Apr 2011

Bibliographical note

Cited By (since 1996):2

Export Date: 1 October 2013

Source: Scopus

CODEN: STCHE

doi: 10.1007/s11224-010-9695-6

Language of Original Document: English

Correspondence Address: Wann, D. A.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, United Kingdom; email: [email protected]

References: Brook, A.G., Abdesaken, F., Gutekunst, B., Gutekunst, G., Kallury, R.K., (1981) J Chem Soc Chem Commun, 191, p. 1981; Shepherd, B.D., Powell, D.R., West, R., (1989) Organometallics, 8, p. 2664. , 10.1021/om00113a024 1:CAS:528:DyaL1MXmtFCmt7o%3D; Goerlich, J.R., Weiss, J.-V., Jones, P.G., Schmutzler, R., (1992) Phosphorus Sulfur Silicon, 66, p. 223. , 10.1080/10426509208038351 1:CAS:528:DyaK38XktVyjtrw%3D; Goerlich, J.R., Schmutzler, R., (1995) Phosphorus Sulfur Silicon, 101, p. 245. , 10.1080/10426509508042523 1:CAS:528:DyaK2MXoslWks7o%3D; Goerlich, J.R., Schmutzler, R., (1995) Phosphorus Sulfur Silicon, 101, p. 245. , 10.1080/10426509508042523 1:CAS:528:DyaK2MXoslWks7o%3D; Patsanovskii, I.I., Yarkova, E.G., Shakirov, I.K., Gulyaeva, Z.R., Ishmaeva, E.A., Muller, S., Schmutzler, R., (1995) Zh Org Khim, 21, p. 1580; Stetter, H., Last, W.D., (1969) Chem Ber, 102, p. 3364; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J Chem Soc Dalton Trans, 954; Lewis, J.R., Brain, P.T., Rankin, D.W.H., (1997) Spectrum, 15, p. 7; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans, 2469; Ross, A.W., Fink, M., Hilderbrandt, R., (1992) International Tables for Crystallography, p. 245. , Wilson AJC (ed) vol C. Kluwer Academic Publishers, Dordrecht, Netherlands; National Service for Computational Chemistry Software (NSCCS), , http://www.nsccs.ac.uk; http://www.eastchem.ac.uk/rcf). ThisfacilityispartiallysupportedbytheeDIKTinitiative, EaStCHEM Research Computing Facility http://www.edikt.org)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, CTBlake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J Phys Chem, 100, p. 12280. , 10.1021/jp960084r 1:CAS:528:DyaK28XjvFCisLY%3D; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J Chem Soc Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650; Sipachev, V.A., (1985) J Mol Struct, 121, p. 143; Sipachev, V.A., Local centrifugal distortions caused by internal motions of molecules (2001) Journal of Molecular Structure, 567-568, pp. 67-72. , DOI 10.1016/S0022-2860(01)00534-8, PII S0022286001005348; Oberhammer, H., Schmutzler, R., Stelzer, O., (1978) Inorg Chem, 17, p. 1254. , 10.1021/ic50183a031 1:CAS:528:DyaE1cXhs1Wqt74%3D; Hinchley, S.L., Haddow, M.F., Rankin, D.W.H., (2004) Dalton Trans, p. 384; Hinchley, S.L., Haddow, M.F., Rankin, D.W.H., (2004) Inorg Chem, 43, p. 5522. , 10.1021/ic049467r 1:CAS:528:DC%2BD2cXmt1Sgtbs%3D; Hinchley, S.L., Smart, B.A., Morrison, C.A., Robertson, H.E., Rankin, D.W.H., Zink, R., Hassler, K., (1999) J Chem Soc Dalton Trans, p. 2303

Keywords

1-Adamantylphosphines
Gas electron diffraction
Molecular structure
Quantum chemical calculations

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10.1007/s11224-010-9695-6

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Cite this

@article{433c3ace35074314b9750ad8b3de0022,

title = "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. {\textcopyright} 2010 Springer Science+Business Media, LLC.",

keywords = "1-Adamantylphosphines, Gas electron diffraction, Molecular structure, Quantum chemical calculations",

author = "D.A. Wann and A.R. Turner and J.R. Goerlich and L.J. Kettle and R. Schmutzler and D.W.H. Rankin",

note = "Cited By (since 1996):2 Export Date: 1 October 2013 Source: Scopus CODEN: STCHE doi: 10.1007/s11224-010-9695-6 Language of Original Document: English Correspondence Address: Wann, D. A.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, United Kingdom; email: [email protected] References: Brook, A.G., Abdesaken, F., Gutekunst, B., Gutekunst, G., Kallury, R.K., (1981) J Chem Soc Chem Commun, 191, p. 1981; Shepherd, B.D., Powell, D.R., West, R., (1989) Organometallics, 8, p. 2664. , 10.1021/om00113a024 1:CAS:528:DyaL1MXmtFCmt7o%3D; Goerlich, J.R., Weiss, J.-V., Jones, P.G., Schmutzler, R., (1992) Phosphorus Sulfur Silicon, 66, p. 223. , 10.1080/10426509208038351 1:CAS:528:DyaK38XktVyjtrw%3D; Goerlich, J.R., Schmutzler, R., (1995) Phosphorus Sulfur Silicon, 101, p. 245. , 10.1080/10426509508042523 1:CAS:528:DyaK2MXoslWks7o%3D; Goerlich, J.R., Schmutzler, R., (1995) Phosphorus Sulfur Silicon, 101, p. 245. , 10.1080/10426509508042523 1:CAS:528:DyaK2MXoslWks7o%3D; Patsanovskii, I.I., Yarkova, E.G., Shakirov, I.K., Gulyaeva, Z.R., Ishmaeva, E.A., Muller, S., Schmutzler, R., (1995) Zh Org Khim, 21, p. 1580; Stetter, H., Last, W.D., (1969) Chem Ber, 102, p. 3364; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J Chem Soc Dalton Trans, 954; Lewis, J.R., Brain, P.T., Rankin, D.W.H., (1997) Spectrum, 15, p. 7; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans, 2469; Ross, A.W., Fink, M., Hilderbrandt, R., (1992) International Tables for Crystallography, p. 245. , Wilson AJC (ed) vol C. Kluwer Academic Publishers, Dordrecht, Netherlands; National Service for Computational Chemistry Software (NSCCS), , http://www.nsccs.ac.uk; http://www.eastchem.ac.uk/rcf). ThisfacilityispartiallysupportedbytheeDIKTinitiative, EaStCHEM Research Computing Facility http://www.edikt.org)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, CTBlake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J Phys Chem, 100, p. 12280. , 10.1021/jp960084r 1:CAS:528:DyaK28XjvFCisLY%3D; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J Chem Soc Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650; Sipachev, V.A., (1985) J Mol Struct, 121, p. 143; Sipachev, V.A., Local centrifugal distortions caused by internal motions of molecules (2001) Journal of Molecular Structure, 567-568, pp. 67-72. , DOI 10.1016/S0022-2860(01)00534-8, PII S0022286001005348; Oberhammer, H., Schmutzler, R., Stelzer, O., (1978) Inorg Chem, 17, p. 1254. , 10.1021/ic50183a031 1:CAS:528:DyaE1cXhs1Wqt74%3D; Hinchley, S.L., Haddow, M.F., Rankin, D.W.H., (2004) Dalton Trans, p. 384; Hinchley, S.L., Haddow, M.F., Rankin, D.W.H., (2004) Inorg Chem, 43, p. 5522. , 10.1021/ic049467r 1:CAS:528:DC%2BD2cXmt1Sgtbs%3D; Hinchley, S.L., Smart, B.A., Morrison, C.A., Robertson, H.E., Rankin, D.W.H., Zink, R., Hassler, K., (1999) J Chem Soc Dalton Trans, p. 2303",

year = "2011",

month = apr,

doi = "10.1007/s11224-010-9695-6",

language = "English",

volume = "22",

pages = "263--267",

journal = "Structural Chemistry",

issn = "1040-0400",

publisher = "Springer",

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TY - JOUR

T1 - Gas-phase structures of 1-adamantylphosphines, PH n (1-Ad) 3-n (n = 1-3)

AU - Wann, D.A.

AU - Turner, A.R.

AU - Goerlich, J.R.

AU - Kettle, L.J.

AU - Schmutzler, R.

AU - Rankin, D.W.H.

N1 - Cited By (since 1996):2 Export Date: 1 October 2013 Source: Scopus CODEN: STCHE doi: 10.1007/s11224-010-9695-6 Language of Original Document: English Correspondence Address: Wann, D. A.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, United Kingdom; email: [email protected] References: Brook, A.G., Abdesaken, F., Gutekunst, B., Gutekunst, G., Kallury, R.K., (1981) J Chem Soc Chem Commun, 191, p. 1981; Shepherd, B.D., Powell, D.R., West, R., (1989) Organometallics, 8, p. 2664. , 10.1021/om00113a024 1:CAS:528:DyaL1MXmtFCmt7o%3D; Goerlich, J.R., Weiss, J.-V., Jones, P.G., Schmutzler, R., (1992) Phosphorus Sulfur Silicon, 66, p. 223. , 10.1080/10426509208038351 1:CAS:528:DyaK38XktVyjtrw%3D; Goerlich, J.R., Schmutzler, R., (1995) Phosphorus Sulfur Silicon, 101, p. 245. , 10.1080/10426509508042523 1:CAS:528:DyaK2MXoslWks7o%3D; Goerlich, J.R., Schmutzler, R., (1995) Phosphorus Sulfur Silicon, 101, p. 245. , 10.1080/10426509508042523 1:CAS:528:DyaK2MXoslWks7o%3D; Patsanovskii, I.I., Yarkova, E.G., Shakirov, I.K., Gulyaeva, Z.R., Ishmaeva, E.A., Muller, S., Schmutzler, R., (1995) Zh Org Khim, 21, p. 1580; Stetter, H., Last, W.D., (1969) Chem Ber, 102, p. 3364; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J Chem Soc Dalton Trans, 954; Lewis, J.R., Brain, P.T., Rankin, D.W.H., (1997) Spectrum, 15, p. 7; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans, 2469; Ross, A.W., Fink, M., Hilderbrandt, R., (1992) International Tables for Crystallography, p. 245. , Wilson AJC (ed) vol C. Kluwer Academic Publishers, Dordrecht, Netherlands; National Service for Computational Chemistry Software (NSCCS), , http://www.nsccs.ac.uk; http://www.eastchem.ac.uk/rcf). ThisfacilityispartiallysupportedbytheeDIKTinitiative, EaStCHEM Research Computing Facility http://www.edikt.org)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, CTBlake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J Phys Chem, 100, p. 12280. , 10.1021/jp960084r 1:CAS:528:DyaK28XjvFCisLY%3D; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J Chem Soc Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650; Sipachev, V.A., (1985) J Mol Struct, 121, p. 143; Sipachev, V.A., Local centrifugal distortions caused by internal motions of molecules (2001) Journal of Molecular Structure, 567-568, pp. 67-72. , DOI 10.1016/S0022-2860(01)00534-8, PII S0022286001005348; Oberhammer, H., Schmutzler, R., Stelzer, O., (1978) Inorg Chem, 17, p. 1254. , 10.1021/ic50183a031 1:CAS:528:DyaE1cXhs1Wqt74%3D; Hinchley, S.L., Haddow, M.F., Rankin, D.W.H., (2004) Dalton Trans, p. 384; Hinchley, S.L., Haddow, M.F., Rankin, D.W.H., (2004) Inorg Chem, 43, p. 5522. , 10.1021/ic049467r 1:CAS:528:DC%2BD2cXmt1Sgtbs%3D; Hinchley, S.L., Smart, B.A., Morrison, C.A., Robertson, H.E., Rankin, D.W.H., Zink, R., Hassler, K., (1999) J Chem Soc Dalton Trans, p. 2303

PY - 2011/4

Y1 - 2011/4

N2 - 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. © 2010 Springer Science+Business Media, LLC.

AB - 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. © 2010 Springer Science+Business Media, LLC.

KW - 1-Adamantylphosphines

KW - Gas electron diffraction

KW - Molecular structure

KW - Quantum chemical calculations

U2 - 10.1007/s11224-010-9695-6

DO - 10.1007/s11224-010-9695-6

M3 - Article

SN - 1040-0400

VL - 22

SP - 263

EP - 267

JO - Structural Chemistry

JF - Structural Chemistry

IS - 2

ER -