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Organoberyllium chemistry

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Structure of "diphenyl beryllium, which has the formula Be3(C6H5)6.[1]

Organoberyllium chemistry involves the synthesis and properties of organometallic compounds featuring the group 2 alkaline earth metal beryllium (Be).[2] The area remains less developed relative to the chemistry of other main-group elements, because Be compounds are toxic and few applications have been found.[3]

Structure

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Homoleptic compounds

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The structure of dimethylberyllium.

The coordination number of Be in organoberyllium compounds ranges from two to four.[4]

Dimethylberyllium and dimethylmagnesium adopts the same structure.[5] Diethylberyllium, however, does not structurally resemble diethylmagnesium (which has the same structure as dimethylmagnesium).[6] This contrast is attributed to the small size of Be relative to its heavier congener Mg: Be is one of the smallest atoms on the periodic table.[7] Dineopentylberyllium and many other dialkyl derivatives has been reported.[8]

The phenyl derivative is represented by trimeric Be3Ph6.[1] A terphenyl derivative is known.[9] With bulky aryl ligands three-coordination is observed, see Be(mesityl)2O(C2H5)2.[8]

Organoberyllium compounds are typically prepared by transmetallation or alkylation of beryllium chloride.[10]

Beryllocene

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This structure of Be(C5H5)2

Beryllocene features both pi- and sigma-bonded cyclopentadienyl ligands.[11][12][13] It is prepared from BeCl2 and potassium cyclopentadienide:

2 K[Cp] + BeCl2 → [Cp]2Be + 2 KCl

Mixed ligand compounds

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Many mixed ligand complexes are simply formed by addition of Lewis bases to diaryl and dialkylberyllium compounds. Many derivatives are known of the type BeR2L2 and BAr2L2 are known where L = thioether, pyridine, NHC,[14] and 1,4-Diazabutadienes.[15] Beryllium forms a variety of complexes with N-hetereocyclic carbenes (NHCs).[16][17][18] Beryllium complexes of cyclic alkyl amino carbene (CAAC) ligands have the formula (CAAC)BeR2). A CAAC ligand coordinates a 2 electron -1 charge into the beryllium center.[19] CAAC has an "amino" substituent and an "alkyl" sp3 carbon atom. CAACs are very good σ donors (higher HOMO) and π acceptors (lower LUMO) compared to NHCs. In addition, the lower heteroatom stability of the carbene center in CAAC compared to NHC results in a lower ΔE.

Coordination of a CAAC ligand to a Be complex with R not limited for coordination with Be

Low oxidation beryllium chemistry

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While Be(II) is one of the common oxidation state for Be, compounds containing Be(I) and Be(0) have been described. The latter is obtained from the CAAC adduct of BeCl2 using KC8.[20]

Be(0)(CAAC)2 (Dipp is 2,6-diisopropylphenyl).

One example of a Be(I)-CAAC complex was prepared by the use of TEMPO ((2,2,6,6-Tetramethylpiperidin-1-yl) oxyl).[21] .

Reaction shown is radical cation reaction from a Be(II) CAAC compound to a Be(I) CAAC compound.

History

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Dimethylberyllium was reported in 1876. A. Atterberg produced this first organoberyllium compound by treatment of dimethylmercury with elemental beryllium.[22] The alkylation of beryllium halides was studied by H. Gilman.[23][10] Early systematic work was conducted by G. E. Coates.[2]

See also

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References

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  1. ^ a b Müller, Matthias; Buchner, Magnus R. (2020-08-06). "Diphenylberyllium Reinvestigated: Structure, Properties, and Reactivity of BePh2, [(12-crown-4)BePh]+, and [BePh3]−". Chemistry: A European Journal. 26 (44): 9915–9922. doi:10.1002/chem.202000259. ISSN 0947-6539. PMC 7496417. PMID 31957173.
  2. ^ a b Coates, G. E.; Morgan, G. L. (1971-01-01), Stone, F. G. A.; West, Robert (eds.), Organoberyllium Compounds, Advances in Organometallic Chemistry, vol. 9, Academic Press, pp. 195–257, doi:10.1016/S0065-3055(08)60052-0, ISBN 9780120311095, retrieved 2022-11-08
  3. ^ Gad, S. C. (2014-01-01), "Beryllium", in Wexler, Philip (ed.), Encyclopedia of Toxicology (Third Edition), Oxford: Academic Press, pp. 435–437, ISBN 978-0-12-386455-0, retrieved 2022-10-27
  4. ^ Nembenna, Sharanappa; Sarkar, Nabin; Sahoo, Rajata Kumar; Mukhopadhyay, Sayantan (2022-01-01), Parkin, Gerard; Meyer, Karsten; O’hare, Dermot (eds.), "2.03 - Organometallic Complexes of the Alkaline Earth Metals", Comprehensive Organometallic Chemistry IV, Oxford: Elsevier, pp. 71–241, ISBN 978-0-323-91350-8, retrieved 2022-10-27
  5. ^ Snow, A. I.; Rundle, R. E. (1951-07-02). "The structure of dimethylberyllium". Acta Crystallographica. 4 (4): 348–352. Bibcode:1951AcCry...4..348S. doi:10.1107/S0365110X51001100. hdl:2027/mdp.39015095081207. ISSN 0365-110X.
  6. ^ Weiss, E. (1965). "Die kristallstruktur des diäthylmagnesiums". Journal of Organometallic Chemistry. 4 (2): 101–108. doi:10.1016/S0022-328X(00)84373-9.
  7. ^ Montero-Campillo, M. Merced; Mó, Otilia; Yáñez, Manuel; Alkorta, Ibon; Elguero, José (2019-01-01), van Eldik, Rudi; Puchta, Ralph (eds.), "Chapter Three - The beryllium bond", Advances in Inorganic Chemistry, Computational Chemistry, vol. 73, Academic Press, pp. 73–121, doi:10.1016/bs.adioch.2018.10.003, S2CID 140062833, retrieved 2022-10-27
  8. ^ a b Ruhlandt-Senge, Karin; Bartlett, Ruth A.; Olmstead, Marilyn M.; Power, Philip P. (1993-04-01). "Synthesis and structural characterization of the beryllium compounds [Be(2,4,6-Me3C6H2)2(OEt2)], [Be{O(2,4,6-tert-Bu3C6H2)}2(OEt2)], and [Be{S(2,4,6-tert-Bu3C6H2)}2(THF)].cntdot.PhMe and determination of the structure of [BeCl2(OEt2)2]". Inorganic Chemistry. 32 (9): 1724–1728. doi:10.1021/ic00061a031. ISSN 0020-1669.
  9. ^ Paparo, Albert; Jones, Cameron (2019-02-01). "Beryllium Halide Complexes Incorporating Neutral or Anionic Ligands: Potential Precursors for Beryllium Chemistry". Chemistry: An Asian Journal. 14 (3): 486–490. doi:10.1002/asia.201801800. ISSN 1861-4728. PMID 30604490. S2CID 58632466.
  10. ^ a b Naglav, Dominik; Buchner, Magnus R.; Bendt, Georg; Kraus, Florian; Schulz, Stephan (2016-08-26). "Off the Beaten Track-A Hitchhiker's Guide to Beryllium Chemistry". Angewandte Chemie International Edition. 55 (36): 10562–10576. doi:10.1002/anie.201601809. PMID 27364901.
  11. ^ Fischer, Ernst Otto; Hofmann, Hermann P. (1959-02-01). "Über Aromatenkomplexe von Metallen, XXV. Di‐cyclopentadienyl‐beryllium". Chemische Berichte. 92 (2): 482–486. doi:10.1002/cber.19590920233. ISSN 0009-2940.
  12. ^ Almenningen, Arne; Haaland, Arne; Lusztyk, Janusz (1979-05-08). "The molecular structure of beryllocene, (C5H5)2Be. A reinvestigation by gas phase electron diffraction". Journal of Organometallic Chemistry. 170 (3): 271–284. doi:10.1016/S0022-328X(00)92065-5. ISSN 0022-328X.
  13. ^ Wong, C.-H.; Lee, T..-Y.; Chao, K.-J.; Lee, S. (1972-06-15). "Crystal structure of bis(cyclopentadienyl)beryllium at –120°C". Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry. 28 (6): 1662–1665. doi:10.1107/S0567740872004820. ISSN 0567-7408.
  14. ^ Thomas-Hargreaves, Lewis R.; Müller, Matthias; Spang, Nils; Ivlev, Sergei I.; Buchner, Magnus R. (2021). "Behavior of Lewis Bases toward Diphenylberyllium". Organometallics. 40 (22): 3797–3807. doi:10.1021/acs.organomet.1c00524.
  15. ^ Paparo, Albert; Best, Stephen P.; Yuvaraj, K.; Jones, Cameron (2020-12-14). "Neutral, Anionic, and Paramagnetic 1,3,2-Diazaberyllacyles Derived from Reduced 1,4-Diazabutadienes". Organometallics. 39 (23): 4208–4213. doi:10.1021/acs.organomet.0c00017. ISSN 0276-7333. S2CID 213828903.
  16. ^ Gilliard, Robert J.; Abraham, Mariham Y.; Wang, Yuzhong; Wei, Pingrong; Xie, Yaoming; Quillian, Brandon; Schaefer, Henry F.; Schleyer, Paul v. R.; Robinson, Gregory H. (2012-06-20). "Carbene-Stabilized Beryllium Borohydride". Journal of the American Chemical Society. 134 (24): 9953–9955. doi:10.1021/ja304514f. ISSN 0002-7863. PMID 22670857.
  17. ^ Paparo, Albert; Jones, Cameron (2019-01-03). "Beryllium Halide Complexes Incorporating Neutral or Anionic Ligands: Potential Precursors for Beryllium Chemistry". Chemistry: An Asian Journal. 14 (3): 486–490. doi:10.1002/asia.201801800. ISSN 1861-4728. PMID 30604490. S2CID 58632466.
  18. ^ Buchner, Magnus R.; Müller, Matthias; Rudel, Stefan S. (2017-01-19). "Beryllium Phosphine Complexes: Synthesis, Properties, and Reactivity of (PMe 3 ) 2 BeCl 2 and (Ph 2 PC 3 H 6 PPh 2 )BeCl 2". Angewandte Chemie International Edition. 56 (4): 1130–1134. doi:10.1002/anie.201610956. PMID 28004465.
  19. ^ Schuster, Julia K.; Roy, Dipak Kumar; Lenczyk, Carsten; Mies, Jan; Braunschweig, Holger (2019-02-18). "New Outcomes of Beryllium Chemistry: Lewis Base Adducts for Salt Elimination Reactions". Inorganic Chemistry. 58 (4): 2652–2658. doi:10.1021/acs.inorgchem.8b03263. ISSN 0020-1669. PMID 30707568. S2CID 73424673.
  20. ^ Arrowsmith, Merle; Braunschweig, Holger; Celik, Mehmet Ali; Dellermann, Theresa; Dewhurst, Rian D.; Ewing, William C.; Hammond, Kai; Kramer, Thomas; Krummenacher, Ivo; Mies, Jan; Radacki, Krzysztof; Schuster, Julia K. (2016-06-06). "Neutral zero-valent s-block complexes with strong multiple bonding". Nature Chemistry. 8 (9): 890–894. Bibcode:2016NatCh...8..890A. doi:10.1038/nchem.2542. ISSN 1755-4349. PMID 27334631.
  21. ^ Wang, Guocang; Walley, Jacob E.; Dickie, Diane A.; Pan, Sudip; Frenking, Gernot; Gilliard, Robert J. (2020-03-11). "A Stable, Crystalline Beryllium Radical Cation". Journal of the American Chemical Society. 142 (10): 4560–4564. doi:10.1021/jacs.9b13777. ISSN 0002-7863. PMID 32088963. S2CID 211262005.
  22. ^ "C. W. Blomstrand, aus Lund, 31. Mai 1876". Berichte der Deutschen Chemischen Gesellschaft. 9: 853–862. 1876. doi:10.1002/cber.187600901256.
  23. ^ Gilman, Henry; Schulze, F. (1927-11-01). "Organoberyllium halides". Journal of the American Chemical Society. 49 (11): 2904–2908. doi:10.1021/ja01410a043. ISSN 0002-7863.
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