Table 2.

EDA‐NOCV results for [Ag{M(CO)₆}₂]⁺ (M=Cr, Mo, W) complexes using Ag⁺ and {M(CO)₆}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 Figure 4).

Energies	Orbital interaction	[Ag]++[Cr(CO)6]2	[Ag]++[Mo(CO)6]2	[Ag]++[W(CO)6]2
ΔE int		−79.8	−86.1	−86.7
ΔE Pauli		158.3	151.2	151.0
ΔE disp		−9.6 (4.0 %)	−10.8 (4.6 %)	−11.5 (4.8 %)
ΔE elstat [a]		−110.7 (46.5 %)	−108.9 (45.9 %)	−108.6 (45.7 %)
ΔE orb [a]		−117.8 (49.5 %)	−117.6 (49.6 %)	−117.6 (49.5 %)
ΔE orb(1) [b]	[TM(CO)6]→Ag+(s)←[TM(CO)6] σ donation	−39.9 (33.9 %)	−42.6 (36.2 %)	−43.6 (37.1 %)
ΔE orb(2) [b]	[TM(CO)6]→Ag+(pσ)←[TM(CO)6] σ donation	−14.1 (12.0 %)	−15.8 (13.4 %)	−16.3 (13.9 %)
ΔE orb(3) [b]	[TM(CO)6]→Ag+(pπ)←[TM(CO)6] π donation	−5.9 (5.0 %)	−6.3 (5.4 %)	−6.3 (5.4 %)
ΔE orb(4) [b]	[TM(CO)6]→Ag+(pπ)←[TM(CO)6] π donation	−5.6 (4.8 %)	−5.7 (4.8 %)	−5.7 (4.8 %)
ΔE orb(5) [b]	[TM(CO)6]←Ag+(dσ)→[TM(CO)6] σ backdonation	−4.4 (3.7 %)	−5.6 (4.8 %)	−6.1 (5.2 %)
ΔE orb(6) [b]	[TM(CO)6]←Ag+(dπ)→[TM(CO)6] π backdonation	−13.5 (11.5 %)	−11.4 (9.7 %)	−10.9 (9.3 %)
ΔE orb(7) [b]	[TM(CO)6]←Ag+(dπ)→[TM(CO)6] π backdonation	−9.9 (8.4 %)	−8.5 (7.2 %)	−8.1 (6.9 %)
ΔE orb(8) [b]	[TM(CO)6]←Ag+(dσ)→[TM(CO)6] σ backdonation	−4.6 (3.9 %)	−4.3 (3.7 %)	−4.1 (3.5 %)
ΔE orb(9) [b	[TM(CO)6]←Ag+(dδ)→[TM(CO)6] δ backdonation	−2.9 (2.5 %)	−2.7 (2.3 %)	−2.5 (2.1 %)
ΔE orb(rest) [b]		−17.0 (14.4 %)	−14.7 (12.5 %)	−14.0 (11.9 %)
q(Ag)		0.75 (0.89)	0.71 (0.81)	0.70 (0.82)

[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.