The MgBr2‐catalyzed formal [3+2] cycloaddition of donor–acceptor activated cyclopropanes with nitrosoarenes offers a novel approach to various structurally diverse isoxazolidines. The reactions, which are experimentally easy to conduct, occur with complete stereospecificity and perfect control of regioselectivity. Product isoxazolidines can be readily transformed into α‐amino lactones by reductive or decarboxylative NO cleavage and subsequent lactonisation, and the N‐aryl bond cleavage is also possible under oxidative conditions.

Reactions of the zinc(I) complex [Zn2(Mesnacnac)2] (Mesnacnac = [(2,4,6-Me3C6H2)NC(Me)]2CH) with solid K3Bi2 dissolved in liquid ammonia yield crystals of the compound K4[ZnBi2]⋅(NH3)12 (1), which contains the molecular, linear heteroatomic [Bi-Zn-Bi](4-) polyanion (1 a). This anion represents the first example of a three-atomic molecular ion of metal atoms being iso(valence)-electronic to CO2 and being synthesized in solution. The analogy of the discrete [Bi-Zn-Bi](4-) anion and the polymeric ∞(1)[(ZnBi4/2)(4-)] unit to monomeric CO2 and polymeric SiS2 is rationalized.

Reactions of ZnMe2 with isocyanates RNCO proceeded with insertion of the isocyanate into the Zn-Me bond, yielding the corresponding heteroleptic amidate complexes [MeZnOC(Me)NR]x (R = i-Pr 1, t-Bu 2) and [{MeZn}4Zn{OC(Me)NC6F5}6] 3 in high yields. In contrast, ZnCp*2 reacts with isocyanates and isothiocyanates with formation of the homoleptic complexes of the type [Zn{OC(Cp*)NR}2]2 (R = Et 4, i-Pr 5) and [Zn{SC(Cp*)Ni-Pr}2]2 6. 1 -6 were characterized by elemental analyses, multinuclear NMR( 1 H, 13 C, 19 F) and IR spectroscopy and by single-crystal X-ray diffraction (1, 2, 5).

Homoleptic zinc complexes of the type L 2 Zn containing monoanionic β-ketoiminate and bis(thiophosphinoyl)methanide substituents were synthesized in almost quantitative yield by reaction

Reactions of the zinc(I) complex [Zn 2 (Mesnacnac) 2 ] (Mesnacnac = [(2,4,6-Me 3 C 6 H 2 )NC(Me)] 2 CH) with solid K 3 Bi 2 dissolved in liquid ammonia yield crystals of the compound K 4 [ZnBi 2 ]·(NH 3 ) 12 (1), which contains the molecular, linear heteroatomic [Bi À Zn À Bi] 4À polyanion (1 a). This anion represents the first example of a three-atomic molecular ion of metal atoms being iso(valence)-electronic to CO 2 and being synthesized in solution. The analogy of the discrete [BiÀ ZnÀBi] 4À anion and the polymeric 1 1 [(ZnBi 4/2 ) 4À ] unit to monomeric CO 2 and polymeric SiS 2 is rationalized.