TY - JOUR
T1 - The nature of the metal-nitric oxide bond in the [M(CN)5(NO)]q (M = Cr, Mn, Fe, Ru, Os, and Co) and trans-[Ru(NH3)4L(NO)]q (L = pyrazine, pyridine, N2, H2O, Cl-, CN-, NO2-) complexes
T2 - A bond-energy decomposition analysis
AU - Lyubimova, Olga
AU - Sizova, Olga V.
AU - Loschen, Christoph
AU - Frenking, Gernot
PY - 2008/9/30
Y1 - 2008/9/30
N2 - A bond-energy decomposition analysis (EDA) has been carried out to investigate the nature of the M{single bond}NO bonding in the pentacyanonitrosyl [Cr(CN)5(NO)]4-, [Mn(CN)5(NO)]3-, [M(CN)5(NO)]2- (M = Fe, Ru, Os), [Co(CN)5(NO)]3- complexes and in the trans-nitrosyltetraammineruthenium [Ru(NH3)4L(NO)]q (L = pyrazine, pyridine, N2, H2O (q = 3); and L = Cl-, CN-, NO2- (q = 2)) complexes. For the pentacyanonitrosyl complexes of Fe, Ru, and Os three fragmentation models have been considered: {M(CN)5}3-⋯{NO}+, {M(CN)5}2-⋯{NO}0, and {M(CN)5}-⋯{NO}-. The results of the EDA show that the linear M{single bond}NO bonds are predominantly covalent with a significant (∼70%) contribution of π orbital interaction between unpaired electrons on the dπ and π*(NO0) orbitals. EDA results point to the correlation between M{single bond}NO and M{single bond}L binding interactions in the trans-[Ru(NH3)4L(NO)]q complexes.
AB - A bond-energy decomposition analysis (EDA) has been carried out to investigate the nature of the M{single bond}NO bonding in the pentacyanonitrosyl [Cr(CN)5(NO)]4-, [Mn(CN)5(NO)]3-, [M(CN)5(NO)]2- (M = Fe, Ru, Os), [Co(CN)5(NO)]3- complexes and in the trans-nitrosyltetraammineruthenium [Ru(NH3)4L(NO)]q (L = pyrazine, pyridine, N2, H2O (q = 3); and L = Cl-, CN-, NO2- (q = 2)) complexes. For the pentacyanonitrosyl complexes of Fe, Ru, and Os three fragmentation models have been considered: {M(CN)5}3-⋯{NO}+, {M(CN)5}2-⋯{NO}0, and {M(CN)5}-⋯{NO}-. The results of the EDA show that the linear M{single bond}NO bonds are predominantly covalent with a significant (∼70%) contribution of π orbital interaction between unpaired electrons on the dπ and π*(NO0) orbitals. EDA results point to the correlation between M{single bond}NO and M{single bond}L binding interactions in the trans-[Ru(NH3)4L(NO)]q complexes.
KW - Bonding energy
KW - Density functional theory
KW - Energy decomposition analysis
KW - Nitrosyl
KW - Transition metal complexes
UR - http://www.scopus.com/inward/record.url?scp=50349086107&partnerID=8YFLogxK
U2 - 10.1016/j.theochem.2008.06.014
DO - 10.1016/j.theochem.2008.06.014
M3 - 文章
AN - SCOPUS:50349086107
SN - 0166-1280
VL - 865
SP - 28
EP - 35
JO - Journal of Molecular Structure: THEOCHEM
JF - Journal of Molecular Structure: THEOCHEM
IS - 1-3
ER -