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. 2013 May 6;2(3):106–114. doi: 10.1002/open.201300009

Table 3.

Energy decomposition analyses [kcal mol−1] and orbital energies ε [eV] for the metal–ligand bonds in monoligated transition-metal complexes M–L[a]

ML ΔE ΔEint ΔVelstat ΔEPauli ΔEoi ΔInline graphic ΔInline graphic[b] ε[dσ] ε[dπ] ε[dδ]
CoNH3− −217.1 −218.4 −110.0 166.3 −274.7 −241.8 −32.9 +1.84 +2.91 +3.99
CoPH3− −240.6 −241.7 -197.9 204.5 −248.2 −123.9 −124.4 +1.67 +1.81 +3.38
CoCO− −280.6 −286.4 −233.4 274.5 −327.5 −141.7 −185.8 +1.34 +1.17 +3.20
RhNH3− −55.5 −56.2 −143.2 202.1 −115.1 −110.8 −4.3 +1.72 +1.83 +2.53
RhPH3− −89.9 −90.3 −269.7 311.7 −132.3 −61.7 −70.6 +1.49 +0.91 +2.20
RhCO− −122.0 −126.0 −273.3 364.1 −216.8 −96.7 −120.1 +1.05 −0.09 +1.56
IrNH3− −85.0 −85.8 −196.9 268.9 −157.8 −142.9 −14.9 +1.54 +2.16 +2.91
IrPH3− −126.5 −127.2 −349.2 396.0 −174.1 −85.9 −88.2 +1.18 +0.73 +2.28
IrCO− −166.3 −171.3 −353.5 461.5 −279.2 −129.6 −149.7 +0.63 −0.26 +1.68
NiNH3 −77.0 −77.3 −116.2 139.8 −100.8 −94.5 −6.3 −3.28 −2.99 −2.21
NiPH3 −88.0 −88.7 −161.3 173.3 −100.7 −50.8 −49.9 −3.79 −3.93 −2.90
NiCO −109.3 −110.4 −171.6 210.3 −149.1 −60.4 −88.7 −4.89 −5.40 −4.14
PdNH3 −21.6 −21.7 −88.0 105.1 −38.8 −34.5 −4.4 −3.46 −3.81 −3.47
PdPH3 −39.4 −39.8 −166.2 190.3 −63.8 −35.3 −28.5 −4.49 −5.29 −4.56
PdCO −47.4 −47.8 −161.4 213.3 −99.7 −48.0 −51.8 −5.28 −6.48 −5.53
PtNH3 −50.1 −50.4 −170.1 211.4 −91.7 −82.0 −9.7 −4.19 −4.46 −3.72
PtPH3 −77.3 −78.9 −273.9 310.3 −115.3 −70.5 −44.8 −4.92 −5.72 −4.53
PtCO −87.9 −88.7 −271.6 356.9 −174.0 −91.6 −82.4 −5.97 −7.28 −5.77
CuNH3+ −70.0 −70.1 −104.5 86.0 −51.7 −41.9 −9.8 −11.80 −12.13 −12.02
CuPH3+ −68.7 −73.5 −101.7 94.0 −65.8 −51.8 −14.0 −11.99 −12.44 −12.15
CuCO+ −50.2 −50.3 −89.8 100.7 −61.2 −38.8 −22.4 −13.7 −14.28 −13.90
AgNH3+ −48.7 −48.7 −73.3 58.8 −34.2 −28.5 −5.8 −12.56 −13.60 −13.57
AgPH3+ −47.9 −51.8 −84.3 81.3 −48.8 −39.9 −8.9 −12.41 −13.67 −13.85
AgCO+ −28.4 −28.6 −59.1 67.2 −36.7 −26.2 −10.6 −14.08 −15.07 −14.86
AuNH3+ −71.4 −71.6 −124.8 123.2 −70.0 −60.3 −9.7 −12.49 −13.32 −12.92
AuPH3+ −84.2 −91.0 −177.9 187.2 −100.3 −80.9 −19.4 −12.52 −13.70 −13.06
AuCO+ −55.0 −55.1 −149.0 188.4 −94.5 −64.9 −29.7 −14.20 −15.53 −14.73

[a] Computed at ZORA-BLYP/TZ2P. See [Eqs. (1)–(3)]. [b] Also includes small contributions from δ orbital interactions, which can only be separated for C∞v-symmetric MCO complexes. There, the δ term amounts at most to 3.5 % of the π term.