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The analogy between ZnR fragments and the hydrogen radical represents a fruitful concept in organometallic synthesis. The organozinc(ii) and -zinc(i) sources ZnMe 2 (Me = methyl) and [Zn 2 Cp* 2 ] (Cp* = pentamethylcyclopentadienyl) provide one-electron fragments ·ZnR (R = Me, Cp*), which can be trapped by transition metal complexes [L  a  M], yielding [L  b  (ZnR)  n  ]. The addition of the dizinc compound [Zn 2 Cp* 2 ] to coordinatively unsaturated [L  a  M] by the homolytic cleavage of the Zn-Zn bond can be compared to the classic oxidative addition reaction of H 2 , forming dihydride complexes [L  a  M(H) 2 ]. It has also been widely shown that dihydrogen coordinates under preservation of the H-H bond in the case of certain electronic properties of the transition metal fragment. The σ-aromatic triangular clusters [Zn 3 Cp* 3 ] + and [Zn 2 CuCp* 3 ] may be regarded as the first indication of this so far unknown, side-on coordination mode of [Zn 2 Cp* 2 ]. With this background in mind the question arises if a series of complexes featuring the Zn 2 M structural motif can be prepared exhibiting a (more or less) intact Zn-Zn interaction, i.e. di-zinc complexes which are analogous to non-classical dihydrogen complexes of the Kubas type. In order to probe this idea, a series of interrelated organozinc nickel and palladium complexes and clusters were synthesized and characterized as model compounds: [Ni(ZnCp*)(ZnMe)(PMe 3 ) 3 ] ( 1 ), [Ni(ZnCp*) 2 (ZnMe) 2 (PMe 3 ) 2 ] ( 2 ), [{Ni(CN  t  Bu) 2 (μ 2 -ZnCp*)(μ 2 -ZnMe)} 2 ] ( 3 ), [Pd(ZnCp*) 4 (CN  t  Bu) 2 ] ( 4 ) and [Pd 3 Zn 6 (PCy 3 ) 2 (Cp*) 4 ] ( 5 ). The dependence of Zn···Zn interactions as a function of the ligand environments and the metal centers was studied. Experimental X-ray crystallographic structural data and DFT calculations support the analogy between dihydrogen and dizinc transition metal complexes.

Zn⋯Zn interactions at nickel and palladium centers