Abstract
The reactions of 1 and 2 equiv of dimethylzinc with 10 different model ligands, each containing two heteroatoms, were investigated at the HF and B3LYP level of theory. As the heteroatom combination is varied, the stability of the A·ZnMe (formed from acidic ligands) and B·ZnMe2 (formed from nonacidic ligands) species will decrease as follows: A-type ligands, NS > SS > NO > NN> OO; B-type ligands, NN > NO > NS > OO > SS. Formation of the A·ZnMe complex is exothermic by ca. −20 kcal/mol when the ligand contains N and/or O and ca. −30 kcal/mol when S is present. ΔEf is a magnitude of order larger (−2 to −9 kcal/mol) for the formation of B·ZnMe2 complexes. Only monometallic A·ZnMe species are capable of complexing with a second equivalent of dimethylzinc to form a bimetallic A·Zn2Me3 species. NBO analyses provide no indication for a bonding Zn−Zn interaction. The 3d orbitals on zinc are not involved in bonding or hyperconjugative interactions in either the mono- or the bimetallic organozinc species. Zinc−carb...
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