TY - JOUR
T1 - Weakly bonded Lewis base adducts of plumbocene and stannocene
T2 - A synthetic and calculational study
AU - Armstrong, David R.
AU - Beswick, Michael A.
AU - Cromhout, Natalie L.
AU - Harmer, Christopher N.
AU - Moncrieff, David
AU - Russell, Christopher A.
AU - Raithby, Paul R.
AU - Steiner, Alexander
AU - Wheatley, Andrew E.H.
AU - Wright, Dominic S.
PY - 1998/7/20
Y1 - 1998/7/20
N2 - The coordination of [(η-Cp)2Pb] and [(η-Cp)2Sn] by bidentate Lewis-base ligands gives the first examples of adducts of neutral p-block metallocenes. Ab initio MO calculations of [(η-Cp)2Pb·TMEDA] (1) (TMEDA = (Me2NCH2)2), [Cp2Pb·4,4′-Me2bipy] (2) (4,4′-Me2bipy = 4,4′-dimethylbipyridine), and the new complex [(η-Cp)2Sn·TMEDA] (3) confirm that despite the presence of longer Pb-N and Sn-N bonds in the solid-state structures of the TMEDA adducts, the association of TMEDA with the metallocenes is more favorable than with 4,4′-Me2bipy. This finding is a consequence of the greater reorganization energy of 4,4′-Me2bipy compared to TMEDA. The low association energies of these species can be rationalized in terms of metal lone pair/ligand lone pair repulsion.
AB - The coordination of [(η-Cp)2Pb] and [(η-Cp)2Sn] by bidentate Lewis-base ligands gives the first examples of adducts of neutral p-block metallocenes. Ab initio MO calculations of [(η-Cp)2Pb·TMEDA] (1) (TMEDA = (Me2NCH2)2), [Cp2Pb·4,4′-Me2bipy] (2) (4,4′-Me2bipy = 4,4′-dimethylbipyridine), and the new complex [(η-Cp)2Sn·TMEDA] (3) confirm that despite the presence of longer Pb-N and Sn-N bonds in the solid-state structures of the TMEDA adducts, the association of TMEDA with the metallocenes is more favorable than with 4,4′-Me2bipy. This finding is a consequence of the greater reorganization energy of 4,4′-Me2bipy compared to TMEDA. The low association energies of these species can be rationalized in terms of metal lone pair/ligand lone pair repulsion.
UR - http://www.scopus.com/inward/record.url?scp=0001492461&partnerID=8YFLogxK
U2 - 10.1021/om980077k
DO - 10.1021/om980077k
M3 - Article
AN - SCOPUS:0001492461
SN - 0276-7333
VL - 17
SP - 3176
EP - 3181
JO - Organometallics
JF - Organometallics
IS - 15
ER -