The Recently Synthesized Dimagnesiabutadiene and the Analogous Dimetalla-Beryllium, -Calcium, -Strontium, and -Barium Compounds.

The 2014 synthesis of the remarkable dimagnesium compound Mg2 [C4 (CH3 )2 (Si(CH3 )3 )2 ](C3 H7 )2 (C4 H8 O)2 may point the way to a new chapter in alkaline earth organometallic chemistry. Accordingly, we have studied the known Mg compound and the analogous Be, Ca, Sr, and Ba structures. Although most of our theoretical predictions come from density functional methods, the latter have been benchmarked using coupled cluster theory including single, double, and perturbative triplet excitations, CCSD(T) using cc-pVTZ basis sets. Among our most important predictions are the energies for dissociation to the butadiene plus the RM-MR [R=(C3 H7 )2 (C4 H8 O)2 ; M=Be, Mg, Ca, Si, and Ba] entities. The most reliable predictions for the dissociation energies are 99-104 (Be), 85-93 (Mg), 90-99 (Ca), 83-92 (Sr), and 83-94 (Ba) kcal mol-1 . Thus, there is reason to anticipate that the four unknown compounds should be achievable synthetically. The predicted metal-metal distances (not single bonds) are 2.89 Å (Mg⋅⋅⋅Mg), 3.46 Å (Ca⋅⋅⋅Ca), 3.75 Å (Sr⋅⋅⋅Sr), and 4.04 Å (Ba⋅⋅⋅Ba). The separated RM-MR compounds have longer M-M distances but genuine metal-metal single bonds. This perhaps counter intuitive result is due to the presence of the bridging carbons in the alkaline earth butadiene compounds. All five compounds incorporate metal-carbon ionic interactions.