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Organoberyllium chemistry

(Redirected from Carbon–beryllium bond)

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

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..[20]

 
This reaction is shown when a CAAC ligand is coordinated with a BeCl2 and using KC8 to form a zero oxidation beryllium complex. This work was done by Prof Braunschweig to create the first neutral Be complex the R group includes Me and (CH2)5 and Dipp is otherwise known as 2,6-diisopropylphenyl.

One example of a Be(I) was a CAAC ligand has been reported in the form of a radical cation.[21] The reduction of Be(II) to Be(I) involved the use of TEMPO ((2,2,6,6-Tetramethylpiperidin-1-yl) oxyl).

 
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 organoBe 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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