Table 3.

EDA‐NOCV results for [Ag{M(CO)₆}₂]⁻ (M=V, Nb, Ta) complexes using Ag⁺ and {M(CO)₆}₂ ²⁻ as interacting fragments at the BP86‐D3(BJ)/TZ2P level. Energy values are given in kcal mol⁻¹. Calculated partial charge q(Ag) given by the NBO method and (in parentheses) the eigenvalues of the orbital interactions (see Figures S5–S7 in the Supporting Information).

Energies	Orbital interaction	[Ag]++[V(CO)6]2 2−	[Ag]++[Nb(CO)6]2 2−	[Ag]++[Ta(CO)6]2 2−
ΔE int		−121.5	−122.2	−122.4
ΔE Pauli		148.7	149.7	164.7
ΔE disp		−15.4 (3.7 %)	−14.8 (3.7)	−15.3 (3.6 %)
ΔE elstat [a]		−269.0 (66.3 %)	−256.9 (65.3 %)	−285.7 (67.4 %)
ΔE orb [a]		−121.5 (30.0 %)	−122.2 (31.0 %)	−122.4 (29 %)
ΔE orb(1) [b]	[M(CO)6]−→Ag+(s)←[M(CO)6]− σ donation	−44.4 (36.5 %)	−49.1 (40.1 %)	−50.0 (40.8 %)
ΔE orb(2) [b]	[M(CO)6]−→Ag+(pσ)←[M(CO)6]− σ donation	−15.6 (12.8 %)	−17.1 (14.0 %)	−17.8 (14.5 %)
ΔE orb(3) [b]	[M(CO)6]−→Ag+(pπ)←[M(CO)6]− π donation	−6.8 (5.6 %)	−7.6 (6.2 %)	−7.2 (6.0 %)
ΔE orb(4) [b]	[M(CO)6]−→Ag+(pπ)←[M(CO)6]− π donation	−5.6 (4.6 %)	−6.7 (5.5 %)	−5.6 (4.6 %)
ΔE orb(5) [b]	[M(CO)6]−←Ag+(dσ)→[M(CO)6]− σ backdonation	−5.2 (4.3 %)	−5.7 (4.6 %)	−6.2 (5.0 %)
ΔE orb(6) [b]	[M(CO)6]−←Ag+(dπ)→[M(CO)n] π backdonation	−13.1 (10.8 %)	−9.1 (7.4 %)	−10.2 (8.3 %)
ΔE orb(7) [b]	[M(CO)6]−←Ag+(dπ)→[M(CO)6]− π backdonation	−9.3 (7.7 %)	−7.7 (6.3 %)	−7.1 (5.8 %)
ΔE orb(8) [b]	[M(CO)6]−←Ag+(dσ)→[M(CO)6]− σ backdonation	−4.4 (3.7 %)	−2.7 (2.2 %)	−3.7 (3.0 %)
ΔE orb(9) [b	[M(CO)6]−←Ag+(dδ)→[M(CO)6]− δ backdonation	−2.9 (2.4 %)	−2.8 (2.3 %)	−2.5 (2.0 %)
ΔE orb(rest) [b]		−14.2 (11.6 %)	−13.7 (11.2 %)	−10.3 (12 %)
q(Ag)		0.73 (0.18)	0.67 (0.18)	0.66 (0.18)

[a] The values in the parentheses show the contribution to the total attractive interaction ΔE _elstat+ΔE _orb+ΔE _disp. [b] The values in parentheses show the contribution to the total orbital interaction ΔE _orb.