Travelling the organometallic road: a Wittig student’s journey from lithium to magnesium and beyond

Organomagnesium clusters: Structure, stability, and bonding in archetypal models

“…Our BP86/TZ2P bond distances in Fig. 1 are also not far from the previously computed MP2/6-31G(d) values [45,46] 3 MgCl, differences being less than few hundredths of an Å. In addition, they are almost identical to previously reported BP86/TZ2P results [47].…”

“…This situation is similar to that found earlier for the corresponding organoalkalimetal clusters [15e19]. The aggregation energies of the organomagnesium monomers are however less stabilizing because the presence of two ligands (e.g., CH 3 MgCl) leads to more steric congestion as compared to only one ligand in the organoalkalimetal systems (e.g., CH 3 Li and CH 3 Na).…”

“…In particular, they have been used in the synthesis of fine chemicals such as additives, plasticizers, drugs, or other high-value items. Examples of versatile organometallic systems in organic synthesis are the polar organometallic compounds having metale carbon bonds, such as organolithium, organoberyllium, organomagnesium, and organozinc compounds [3]. Grignard reagents [4,5], RMgX (R ¼ alkyl or aryl; X ¼ halogen), are especially relevant since they can be used, amongst others, to introduce functional groups or to form new carbonecarbon bonds in cross-coupling reactions (eq (1)).…”

Bis(allyl)calcium

“…In contrast to the widely employed organomagnesium and organolithium compounds,1, 2 the σ and π complexes of the heavier alkaline earth metals calcium, strontium, and barium3 have not achieved their full potential. Whereas the chemistry of cyclopentadienyl (Cp) calcium compounds is fairly well developed, that of Cp‐free alkyl,4 alkynyl,5 aryl,6 benzyl,7 indenyl,8 and fluorenyl9 calcium compounds has just begun unfolding.…”

Alkaline Earth Organometallics

“…Diethyl ether was most effective; stronger solvation favored the dismutation reaction to dialkylmagnesium. 93 The regioselective synthesis of 1,4-Bu t 2 -2,5-bis(chloromagnesio)benzene 20 was conducted by treating 1,5-bis(chloromercurio)-1,4-di-tert-butylbenzene with methylmagnesium chloride (eqn [6]). 82 In toluene, primary (Bu n ) and secondary (Bu i , Pr i ) alkyl chlorides can be converted into Grignard reagents in good yields if a small amount of ether is present (less than one mole per mole of halide).…”