Various methods for the preparation of organozinc compounds have been reported. [3] However, polyfunctional zinc reagents of type RZnX (X = halide) [4] or R 2 Zn are highly sensitive to moisture and air. These properties represent a serious drawback for their practical use in the laboratory and on an industrial scale. Thus, the availability of more easy to handle organozinc compounds is highly desirable. Since their reactivity is strongly influenced by the presence of salts, [5] we anticipated that the presence of appropriate metallic salts may lead to an improved stability towards air and water. Charette et al. have already demonstrated that alkoxides greatly stabilize zinc carbenoids for enantioselective cyclopropanations.[6] Furthermore, Herrmann et al. reported that methylzinc acetate can be efficiently used for the synthesis of methyltrioxorhenium (MTO), even on large scales. [7] Herein, we report the preparation of solid salt-stabilized functionalized aryl, heteroaryl, and benzylic zinc reagents of the general formula RZnOPiv·Mg(OPiv)(X)·2 LiCl (X = Cl, Br, or I; OPiv = pivalate; abbreviated RZnOPiv for clarity). These new zinc reagents are readily prepared by a one-pot synthesis in which the organic halide (RX; X = Cl, Br) is treated with magnesium turnings (2.5 equiv) [8] and the THFsoluble salt Zn(OPiv) 2 ·2 LiCl [9] (2; 1.5 equiv). Under these conditions, the formation of the zinc reagent is observed at 25 8C within 2 h.[10] The presence of Zn(OPiv) 2 ·2 LiCl (2) not only stabilizes the resulting zinc reagent, but also accelerates its formation dramatically. Whereas 4-bromo-1,2-dimethylbenzene (1 a) requires 2 h in the presence of Mg/ ZnCl 2 ·2 LiCl, [8] the insertion reaction is complete within 20 min when using the combination Mg/Zn(OPiv) 2 ·2 LiCl (2). After evaporation of the solvent, the corresponding solid organozinc pivalate 3 a is obtained in 77 % yield.[11] This rate acceleration is essential for tolerating sensitive functional groups. This route is widely applicable and after evaporation of the THF, the resulting solid arylzinc reagents are obtained in 57-84 % yield as easy to handle powders (Scheme 1). This is in contrast to regular zinc reagents which produce only highly viscous oils when the solvents are evaporated.By using this method we have prepared a range of arylzinc reagents bearing electron-donating substituents (3 a-f; FG = Me, OMe, SMe, OTIPS, TMS, OCONEt 2 ; 57-81 %) or electron-deficient substituents (3 g-j; FG = F, CF 3 , CO 2 Et, CN; 59-84 %; Scheme 1). Although the ester-and nitrilesubstituted zinc reagents 3 i and 3 j can be prepared in satisfactory yields (59-64 %) by direct insertion, an improvement has been achieved by using an I/Mg or Br/Mg exchange with iPrMgCl·LiCl followed by transmetalation with Zn(OPiv) 2 ·2 LiCl (2; 72-89 %). [12] Moreover, the solid zinc reagents of type 3 are stable under argon at room temperature for several months without significant loss of activity. Importantly, these zinc compounds can now be weighed in air (95 % of the active zinc specie...