Organoberyllium chemistry

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Structure of diphenylberyllium, which has the formula .mw-parser-output .template-chem2-su{display:inline-block;font-size:80%;line-height:1;vertical-align:-0.35em}.mw-parser-output .template-chem2-su>span{display:block;text-align:left}.mw-parser-output sub.template-chem2-sub{font-size:80%;vertical-align:-0.35em}.mw-parser-output sup.template-chem2-sup{font-size:80%;vertical-align:0.65em} Be3(C6H5)6. Crystal Structure of a BePh2 Complex that produce dimers.png
Structure of diphenylberyllium, which has the formula Be3(C6H5)6.

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]

Contents

Structure

Homoleptic compounds

The structure of dimethylberyllium. Me2Be.svg
The structure of dimethylberyllium.

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

Dimethylberyllium and dimethylmagnesium adopt 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

This structure of Be(C5H5)2 Beryllocene conformation.svg
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

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]

Low oxidation beryllium chemistry

While the +2-oxidation state is by far the most common for Be, compounds containing Be(I) and Be(0) have been described. A number of beryllium complexes with cyclic alkyl amino carbene  (CAAC) ligands have been proposed to feature low-oxidation state beryllium centres. [19] [20] However, these low-oxidation state formulations have been contested due to the redox non-innocence of CAAC ligands. [21] [22] [23] Unambiguous low-oxidation state organo-beryllium complexes with Be–Be bonds have been synthesized by the group of Simon Aldridge. [24] [25]

History

Dimethylberyllium was reported in 1876. A. Atterberg produced this first organoberyllium compound by treatment of dimethylmercury with elemental beryllium. [26] The alkylation of beryllium halides was studied by H. Gilman. [27] [10] Early systematic work was conducted by G. E. Coates. [2]

See also

References

  1. 1 2 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. 1 2 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. 1 2 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. 1 2 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. ↑ 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.
  20. ↑ 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.
  21. ↑ Gimferrer, Martí; Danés, Sergi; Vos, Eva; Yildiz, Cem B.; Corral, Inés; Jana, Anukul; Salvador, Pedro; Andrada, Diego M. (2022-06-07). "The oxidation state in low-valent beryllium and magnesium compounds". Chemical Science. 13 (22): 6583–6591. doi:10.1039/D2SC01401G. hdl: 10486/706893 . ISSN   2041-6539. PMC   9172369 .
  22. ↑ Gimferrer, Martí; Danés, Sergi; Vos, Eva; Yildiz, Cem B.; Corral, Inés; Jana, Anukul; Salvador, Pedro; Andrada, Diego M. (2023-01-04). "Reply to the 'Comment on "The oxidation state in low-valent beryllium and magnesium compounds"' by S. Pan and G. Frenking, Chem. Sci., 2022, 13, DOI: 10.1039/D2SC04231B". Chemical Science. 14 (2): 384–392. doi:10.1039/D2SC05769G. hdl: 10486/712698 . ISSN   2041-6539. PMC   9811512 .
  23. ↑ Parkin, Gerard (2022-01-04). "Impact of the coordination of multiple Lewis acid functions on the electronic structure and vn configuration of a metal center" . Dalton Transactions. 51 (2): 411–427. doi:10.1039/D1DT02921E. ISSN   1477-9234.
  24. ↑ Boronski, Josef T.; Crumpton, Agamemnon E.; Wales, Lewis L.; Aldridge, Simon (2023-06-16). "Diberyllocene, a stable compound of Be(I) with a Be–Be bond" . Science. 380 (6650): 1147–1149. doi:10.1126/science.adh4419.
  25. ↑ Boronski, Josef T.; Crumpton, Agamemnon E.; Roper, Aisling F.; Aldridge, Simon (August 2024). "A nucleophilic beryllyl complex via metathesis at [Be–Be]2+". Nature Chemistry. 16 (8): 1295–1300. doi:10.1038/s41557-024-01534-9. ISSN   1755-4349. PMC   11321998 .
  26. ↑ "C. W. Blomstrand, aus Lund, 31. Mai 1876". Berichte der Deutschen Chemischen Gesellschaft. 9: 853–862. 1876. doi:10.1002/cber.187600901256.
  27. ↑ 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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