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Organoberyllium chemistry involves the synthesis and properties of organometallic compounds featuring the group 2 alkaline earth metal beryllium (Be). 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.

Structure

Homoleptic compounds

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

Dimethylberyllium and dimethylmagnesium adopts the same structure. Diethylberyllium, however, does not structurally resemble diethylmagnesium (which has the same structure as dimethylmagnesium). 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. Dineopentylberyllium and many other dialkyl derivatives has been reported.

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

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

Beryllocene

Beryllocene features both pi- and sigma-bonded cyclopentadienyl ligands. 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, and 1,4-Diazabutadienes. Beryllium forms a variety of complexes with N-hetereocyclic carbenes (NHCs). 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. CAAC has an "amino" substituent and an "alkyl" sp 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.

Low oxidation beryllium chemistry

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 cyclic alkyl amino carbene (CAAC) adduct of BeCl₂ using KC₈.

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

History

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

See also

• Group 2 organometallic chemistry
• Beryllium

References

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v t e Compounds of carbon with other elements in the periodic table
CH He CLi CBe CB CC CN CO CF Ne CNa CMg CAl CSi CP CS CCl CAr CK CCa CSc CTi CV CCr CMn CFe CCo CNi CCu CZn CGa CGe CAs CSe CBr CKr CRb CSr CY CZr CNb CMo CTc CRu CRh CPd CAg CCd CIn CSn CSb CTe CI CXe CCs CBa CLu CHf CTa CW CRe COs CIr CPt CAu CHg CTl CPb CBi CPo CAt Rn Fr CRa Lr Rf Db CSg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og   CLa CCe CPr CNd CPm CSm CEu CGd CTb CDy CHo CEr CTm CYb Ac CTh CPa CU CNp CPu CAm CCm CBk CCf CEs Fm Md No
Legend	Chemical bonds to carbon Core organic chemistry Many uses in chemistry Academic research, no widespread use Bond unknown

• Beryllium compounds
• Organometallic chemistry