Abstract
Density functional theory (DFT) calculations have been carried out on four novel dicoordinated lead compounds PbL2 where L is an N-heterocyclic ylidene or a five-membered cyclic ylidene (1Pb, 2Pb, 4Pb, 5Pb) and for a plumbylene-coordinated carbone CL2 (3Pb). The theoretically predicted equilibrium geometries and the first and second proton affinities of 1Pb–5Pb are reported. Geometry optimizations have also been carried out for the complexes with one and two BH3 ligands 1Pb(BH 3 )–5Pb(BH 3 ) and 1Pb(BH 3 ) 2 –5Pb(BH 3 ) 2 , and for the transition metal complexes 1PbW(CO) 5 –5PbW(CO) 5 and 1PbNi(CO) 3 –5PbNi(CO) 3 . The results suggest that the molecules 1Pb, 2Pb and 4Pb possess properties which identify them as divalent Pb(0) compounds (plumbylones). This comes to the fore by the theoretically predicted second PAs which are very large for a lead compound and (for 1Pb and 4Pb) by the BDE of the second BH3 ligand. Compound 3Pb should be considered as a plumbylene-coordinated divalent C(0) compound (carbone) which has a very high second PA of 195.1 kcal/mol. The geometry optimization of 5Pb gives an equilibrium structure which identifies the molecules as divalent Pb(II) compound, i.e., as a plumbylene.
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Notes
There are no genuine σ or π orbitals in 1Pb–5Pb because the molecules have no mirror plane. However, the shape of the MOs resembles σ- or π-type orbitals which are symmetric or antisymmetric with respect to a local plane of the central E–E′–E moiety.
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This work was supported by the Deutsche Forschungsgemeinschaft.
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Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.
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Takagi, N., Frenking, G. Divalent Pb(0) compounds. Theor Chem Acc 129, 615–623 (2011). https://doi.org/10.1007/s00214-011-0909-9
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DOI: https://doi.org/10.1007/s00214-011-0909-9