DOI: 10.1002/anie.199504781. The First Unambiguous Characterization of a Neutral Phosphorus Ylide–Lithium Complex: Isolation, Structure, and Ab Initio Investigations of [(PhCH2)2NLi · CH2PPh3]2

The First Unambiguous Characterization of a Neutral Phosphorus Ylide–Lithium Complex: Isolation, Structure, and Ab Initio Investigations of [(PhCH2)2NLi · CH2PPh3]2

10.1002/anie.199504781

Crossref journal-article

Wiley

Angewandte Chemie International Edition in English (311)

Abstract

A four‐membered ring of two lithium and two nitrogen atoms is in the central unit of the dimer in the title (1), a complex between an alkali metal and a neutral phosphorus ylide. Surprisingly, this is the first time that such a model complex for the generation of ylides from phosphonium salts and alkali metal bases has been characterized in the solid state. The structure in solution was also determined, and the complexation energies for this and other model complexes were estimated by ab initio calculations. equation image

Bibliography

Armstrong, D. R., Davidson, M. G., & Moncrieff, D. (1995). The First Unambiguous Characterization of a Neutral Phosphorus YlideâLithium Complex: Isolation, Structure, and Ab Initio Investigations of [(PhCH2)2NLi Â· CH2PPh3]2. Angewandte Chemie International Edition in English, 34(4), 478â481. Portico.

Authors 3

David R. Armstrong (first)
Matthew G. Davidson (additional)
David Moncrieff (additional)

References 34 Referenced 45

10.1126/science.207.4426.42
10.1021/cr00094a007
10.1021/ar50086a003
10.1002/ange.19830951205
10.1002/anie.198309071
{'key': 'e_1_2_1_3_5', 'volume-title': 'Ylides and Imines of Phosphorus', 'author': 'Johnson A. W.', 'year': '1993'} / Ylides and Imines of Phosphorus by Johnson A. W. (1993)
See ref. [3c] chapter 4.
10.1016/S0065-3055(08)60418-9
10.1016/S0065-3055(08)60028-3
10.1016/S0898-8838(08)60005-7
D. R.Armstrong S.Bennet M. G.Davidson R.Snaith D.Staike D. S.Wright J. Chem. Soc. Chem. Commun.1992 262.
(a)D.Barr W.Clegg R. E.Mulvey R.Snaith J. Chem. Soc. Chem. Commun.1984 285. (10.1039/C39840000285)
(b)J. Chem. Soc. Chem. Commun.1984 287.
(a)J. C. J.Bart J. Chem. Soc. B1969 350;
{'key': 'e_1_2_1_8_3', 'first-page': '341', 'volume': '13', 'author': 'Schmidbaur H.', 'year': '1989', 'journal-title': 'New J. Chem.'} / New J. Chem. by Schmidbaur H. (1989)
X‐ray crystal data for3: C33H31LiNP Mr= 479.50 triclinic space groupP1 a= 9.689(2) b= 10.871(2) c= 12.731(3) Å α = 92.17(3) β = 95.84(3) γ = 96.97(3)° V= 1322.4(5) Å3 Z= 2 ρcalcd.= 1.204 Mg m3 F(000) = 508 μ(MoKα) = 0.71073 Å μ(MoKα) = 0.126 mm−1 T= 153(2) K. Data were collected on a Stoe four‐circle diffractometer in the range 7° ≤ 2θ ≤ 45° (4685 reflections were collected of which 3455 were independent Rint= 0.0189). The structure was solved by direct methods [18] and refinement based onF2 was by full‐matrix least‐squares techniques [19] (all non‐hydrogen atoms were refined anisotropically; H atoms except H61a and H61b which were located and refined freely were placed in calculated positions) toR1= 0.0367 wR2= 0.0964 for 3036 unique reflections for whichF> 4°(F). Further details of the crystal structure are available on request from the Director of the Cambridge Crystallographic Data Centre 12 Union Road Cambridge CB21EZ (UK) on quoting the full journal citation.
10.1021/om00138a034
{'key': 'e_1_2_1_11_2', 'first-page': '612', 'volume': '114', 'author': 'Schmidbaur H.', 'year': '1981', 'journal-title': 'Chem. Ber.'} / Chem. Ber. by Schmidbaur H. (1981)
10.1021/om00097a003
10.1021/jo00062a026
10.1002/cber.19861190421
10.1021/cr00029a008
Ab initio MO calculations: 6–31G basis set [20a] with d orbitals on P atoms at the SCF level (monomeric complexes) 6–31G**basis set the at the MP2 level [20b] (dimeric complexes) using the programs GAMESS [20c] and GAUSSIAN 92. [20d] All geometries were freely optimised. A manuscript for publication elsewhere is in preparation in which full details of all calculations performed will be given.
10.1021/cr00029a006
10.1002/cber.19721050340
10.1107/S0108767390000277
G. M.Sheldrick SHELXL‐93 Program for crystal structure refinement University of Göttingen 1993.
10.1063/1.1677527
10.1007/BF00533485
10.1016/0009-2614(80)80628-2
10.1103/PhysRev.46.618
(c)M.Dupuis D.Spangler J. J.Wendoloski NRCC Software Catalogue Program No. QGZ1 (GAMESS);
M. F.Guest P.Fantucci R. J.Harrison J.Kendrick J. H.van Lenthe K.Schoeffel P.Sherwood GAMESS UK (CFS Ltd. 1993);
(d)M. J.Frisch G. W.Trucks M.Head‐Gordon P. M. W.Gill M. W.Wong J. B.Foresman B. G.Johnson H. B.Schleger M. A.Robb E. S.Repogle R.Gomperts J. L.Andres K.Raghavachari J. S.Binkley C.Gonzalez R. L.Martin D.Fox D. L.Defrees J.Baker J. J. P.Stewart J. A.Pople Gaussian Inc. Pittsburgh PA 1992.

Dates

Type	When
Created	21 years, 7 months ago (Dec. 31, 2003, 3:39 a.m.)
Deposited	1 year, 9 months ago (Oct. 25, 2023, 5:15 p.m.)
Indexed	11 months, 1 week ago (Sept. 16, 2024, 2:30 p.m.)
Issued	30 years, 5 months ago (March 7, 1995)
Published	30 years, 5 months ago (March 7, 1995)
Published Online	21 years, 8 months ago (Dec. 22, 2003)
Published Print	30 years, 5 months ago (March 7, 1995)

Funders 0

None

BibTeX

@article{Armstrong_1995, title={The First Unambiguous Characterization of a Neutral Phosphorus Ylide–Lithium Complex: Isolation, Structure, and Ab Initio Investigations of [(PhCH2)2NLi · CH2PPh3]2}, volume={34}, ISSN={0570-0833}, url={http://dx.doi.org/10.1002/anie.199504781}, DOI={10.1002/anie.199504781}, number={4}, journal={Angewandte Chemie International Edition in English}, publisher={Wiley}, author={Armstrong, David R. and Davidson, Matthew G. and Moncrieff, David}, year={1995}, month=mar, pages={478–481} }

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