Something to zinc about: A base‐stabilized [Zn2]2+ dication, obtained from the reaction of [Cp*2Zn2(dmap)2] (Cp*=C5Me5, dmap=4‐dimethylaminopyridine) with two equivalents of [H(OEt2)2][Al{OC(CF3)3}4], is structurally characterized for the first time (see structure; red Zn, blue N, gray C; ZnZn 2.419(1) Å).

The reaction of decamethyldizincocene Cp*2Zn2 1 with MesnacnacH proceeds with protonation of the Cp* substituent and subsequent formation of the zinc-zinc bonded complex (Mesnacnac)2Zn2 3.

Group 13-group 13 donor-acceptor complexes Cp*M-Al(t-Bu) 3 (M ) Al 1, Ga 2, In 3) and Cp*M-Ga(t-Bu) 3 (M ) Al 4, Ga 5, In 6) were obtained from reactions between [Cp*M] x (M ) Al, x ) 4; Ga, In, x ) 6) and M(t-Bu) 3 (M ) Al, Ga). 3, 4, and 6 represent the first compounds containing dative In(I)-Al(III), Al(I)-Ga(III), and In(I)-Ga(III) bonds. 1-6 were characterized by elemental analyses, mass and multinuclear NMR spectroscopy ( 1 H, 13 C), and single-crystal X-ray analysis (except for 5).Supporting Information Available: Tables of bond distances, bond angles, anisotropic temperature factor parameters, and fractional coordinates for 1, 2, 3, 4, and 6. This material is available free of charge via the Internet at http://pubs.acs.org. OM0606946

Reactions of Cp*(2)Zn(2) with sterically demanding bis(iminodi(phenyl)phosphorano)methanes LH (LH = CH(2)(Ph(2)P=NR)(2) (R = Ph L(1)H, SiMe(3)L(2)H, 2,6-i-Pr(2)C(6)H(3) (Dipp) L(3)H) at ambient temperature occurred with elimination of Cp*H and subsequent formation of the homoleptic complex L(1)(2)Zn(2)1 and the heteroleptic complexes LZnZnCp* (L = L(2)2, L(3)3, L(1)4). 3 is the first structurally characterized heteroleptic organozinc complex with the zinc atoms in the formal oxidation state +1.

Reaction without ZnZn rupture: [${{{\rm {\rm Cp}}{{{\ast}\hfill \atop 2\hfill}}}}$Zn2] reacts with a fourfold excess of the strong Lewis base 4‐dimethylaminopyridine (dmap) to unexpectedly form the Lewis acid–base adduct 1, in which both dmap molecules coordinate in a geminal binding mode to only one zinc atom. Cp*=C5Me5.

[MesnacnacZn(µ-H)] 2 (1) was synthesized by reaction of MesnacnacZnI with either an equimolar amount of KNH(iPr)BH 3 or an excess of NaH and characterized by multinuclear NMR and IR spectroscopy as well as X-ray diffraction. Two polymorphs of 1 were found and their structures determined on single crystals.

Tetraalkyldistibanes Sb 2 R 4 (R = nPr, iBu) react with tBu 3 M (M = Al, Ga) at -30°C with the formation of the Lewis acidbase adducts [ iPr 4)]. Compounds 1 and 2 are stable in solution whereas 3 undergoes a Sb-Sb bond-breakage reaction with the subsequent formation of [tBu 2 GaSb(nPr) 2 ] 2 (5). The same trend was observed for the reaction of Sb 2 (iBu) 4 with tBu 3 Ga, which yielded the heterocyclic stibanylgallane

Eine unerwartete Reaktion: [${{{\rm {\rm Cp}}{{{\ast}\hfill \atop 2\hfill}}}}$Zn2] reagiert mit der starken Lewis‐Base 4‐Dimethylaminopyridin (dmap) in vierfachem Überschuss zum unerwarteten Lewis‐Säure‐Base‐Addukt 1, in dem zwei dmap‐Moleküle unter Erhaltung der Zn‐Zn‐Bindung geminal an ein Zn‐Zentrum binden. Cp*=C5Me5.