TY - JOUR
T1 - Divalent Pb(0) compounds
AU - Takagi, Nozomi
AU - Frenking, Gernot
PY - 2011/6
Y1 - 2011/6
N2 - 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(BH3)-5Pb(BH3) and 1Pb(BH3)2-5Pb(BH3)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.
AB - 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(BH3)-5Pb(BH3) and 1Pb(BH3)2-5Pb(BH3)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.
KW - DFT calculations
KW - Divalent Pb(0) compounds
KW - Plumbylone
KW - Proton affinity
KW - Transition metal complexes
UR - http://www.scopus.com/inward/record.url?scp=79955929391&partnerID=8YFLogxK
U2 - 10.1007/s00214-011-0909-9
DO - 10.1007/s00214-011-0909-9
M3 - 文章
AN - SCOPUS:79955929391
SN - 1432-881X
VL - 129
SP - 615
EP - 623
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 3-5
ER -