TY - JOUR
T1 - Trends in back-bonding in the series trans-[M(C≡CR)Cl(PH3)4] (M = Fe, Ru, Os; R = H, Ph, C6H4NO2-4)
AU - Delfs, Christopher D.
AU - Stranger, Rob
AU - Humphrey, Mark G.
AU - McDonagh, Andrew M.
PY - 2000/8/11
Y1 - 2000/8/11
N2 - The electronic structure of the complexes trans-[M(C≡CR)Cl(PH3)4] (M = Fe, Ru, Os; R = H, Ph, C6H4NO2-4) has been investigated using approximate density functional theory in order to examine the M-C back-bonding interaction. For all three metal systems, the π back-bonding increases in the order R = H < Ph < C6H4-4-NO2, indicating that the π acceptor character of the acetylide ligand increases with the electron-withdrawing ability of the substituent. The inclusion of relativistic effects in the calculations results in a metal dependence of Fe ∼ Ru < Os for the back-bonding, consistent with the observed trend in quadratic hyperpolarizabilities, β.
AB - The electronic structure of the complexes trans-[M(C≡CR)Cl(PH3)4] (M = Fe, Ru, Os; R = H, Ph, C6H4NO2-4) has been investigated using approximate density functional theory in order to examine the M-C back-bonding interaction. For all three metal systems, the π back-bonding increases in the order R = H < Ph < C6H4-4-NO2, indicating that the π acceptor character of the acetylide ligand increases with the electron-withdrawing ability of the substituent. The inclusion of relativistic effects in the calculations results in a metal dependence of Fe ∼ Ru < Os for the back-bonding, consistent with the observed trend in quadratic hyperpolarizabilities, β.
KW - Density functional theory
KW - Metal-carbon backbonding
KW - Relativistic effects
UR - http://www.scopus.com/inward/record.url?scp=0001640186&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)00349-1
DO - 10.1016/S0022-328X(00)00349-1
M3 - Article
SN - 0022-328X
VL - 607
SP - 208
EP - 212
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -