Table 4. Numerical EDA-NOCV Results of the Charged Carbonyl Complexes [M(CO)n]q at the M06/TZ2P//M06-D3/def2-TZVPP Level Using the Charged Metals Mq and Neutral (CO)n in Their Electronic Singlet (S) State as Interacting Moietiesa.
| orbital interactionb | interacting fragments | |||
|---|---|---|---|---|
| [Ir(CO)6]3+ | ||||
| Ir3+ (S) + (CO)6 (S) | ||||
| ΔEint | –718.0 | |||
| ΔEmetahybrid | 105.8 | |||
| ΔEPauli | 405.4 | |||
| ΔEelstatd | –334.2 (27.2%) | |||
| ΔEorbd | –894.9 (72.8%) | |||
| ΔEorb(1) (t2g)e | [M(d)] → (CO)6 π-backdonation | –70.4 (7.9%) | ||
| ΔEorb(2) (eg)e | [M(d)] ← (CO)6 σ-donation | –500.4 (55.9%) | ||
| ΔEorb(3) (a1g)e | [M(s)] ← (CO)6 σ-donation | –73.8 (8.2%) | ||
| ΔEorb(4) (t1u)e | [M(p)] ← (CO)6 σ-donation | –105.2 (11.8%) | ||
| ΔEorb(rest)e | –145.1 (16.2%) | |||
| [M(CO)6]2+ | ||||
| Fe2+ (S) + (CO)6 (S) | Ru2+ (S) + (CO)6 (S) | Os2+ (S) + (CO)6 (S) | ||
| ΔEint | –398.1 | –415.2 | –469.3 | |
| ΔEmetahybrid | 84.5 | 78.2 | 89.1 | |
| ΔEPauli | 286.5 | 384.7 | 428.4 | |
| ΔEelstatd | –202.5 (26.3%) | –283.5 (32.3%) | –341.0 (34.6%) | |
| ΔEorbd | –566.6 (73.7%) | –594.6 (67.7%) | –645.8 (65.4%) | |
| ΔEorb(1) (t2g)e | [M(d)] → (CO)6 π-backdonation | –92.4 (16.3%) | –92.5 (15.6%) | –111.1 (17.2%) |
| ΔEorb(2) (eg)e | [M(d)] ← (CO)6 σ-donation | –302.0 (53.3%) | –340.3 (57.2%) | –339.3 (52.5%) |
| ΔEorb(3) (a1g)e | [M(s)] ← (CO)6 σ-donation | –30.9 (5.5%) | –29.2 (4.9%) | –46.2 (7.2%) |
| ΔEorb(4) (t1u)e | [M(p)] ← (CO)6 σ-donation | –68.7 (12.1%) | –56.3 (9.5%) | –63.4 (9.8%) |
| ΔEorb(rest)e | –72.6 (12.8%) | –76.3 (12.8%) | –85.8 (13.3%) | |
| [M(CO)6]+ | ||||
| Mn+ (S) + (CO)6 (S) | Tc+ (S) + (CO)6 (S) | Re+ (S) + (CO)6 (S) | ||
| ΔEint | –303.2 | –317.1 | –391.4 | |
| ΔEmetahybrid | 73.8 | 67.7 | 69.2 | |
| ΔEPauli | 316.0 | 398.2 | 434.9 | |
| ΔEelstatd | –235.2 (33.9%) | –301.5 (38.5%) | –359.6 (40.2%) | |
| ΔEorbd | –457.7 (66.1%) | –481.5 (61.5%) | –535.9 (59.8%) | |
| ΔEorb(1) (t2g)e | [M(d)] → (CO)6 π-backdonation | –180.0 (39.3%) | –174.1 (36.2%) | –191.4 (35.7%) |
| ΔEorb(2) (eg)e | [M(d)] ← (CO)6 σ-donation | –196.1 (42.8%) | –225.6 (46.9%) | –235.1 (43.9%) |
| ΔEorb(3) (a1g)e | [M(s)] ← (CO)6 σ-donation | –14.3 (3.1%) | –15.4 (3.2%) | –28.0 (5.2%) |
| ΔEorb(4) (t1u)e | [M(p)] ← (CO)6 σ-donation | –32.7 (7.1%) | –29.0 (6.0%) | –34.7 (6.5%) |
| ΔEorb(rest)e | –34.6 (7.6%) | –37.4 (7.8%) | –46.7 (8.7%) | |
| [M(CO)6]− | ||||
| V– (S) + (CO)6 (S) | Nb– (S) + (CO)6 (S) | Ta– (S) + (CO)6 (S) | ||
| ΔEint | –523.4 | –402.9 | –473.7 | |
| ΔEmetahybrid | 30.2 | 42.8 | 32.7 | |
| ΔEPauli | 318.6 | 373.6 | 390.6 | |
| ΔEelstatd | –328.4 (37.7%) | –333.8 (40.7%) | –384.7 (42.9%) | |
| ΔEorbd | –543.8 (62.3%) | –485.5 (59.3%) | –512.3 (57.1%) | |
| ΔEorb(1) (t2g)e | [M(d)] → (CO)6 π-backdonation | –448.7 (82.5%) | –346.6 (71.4%) | –349.5 (68.2%) |
| ΔEorb(2) (eg)e | [M(d)] ← (CO)6 σ-donation | –82.8 (15.2%) | –109.1 (22.5%) | –118.3 (23.1%) |
| ΔEorb(3) (a1g)e | [M(s)] ← (CO)6 σ-donation | –0.5 (0.1%) | –5.4 (1.1%) | –12.3 (2.4%) |
| ΔEorb(4) (t1u)e | [M(p)] ← (CO)6 σ-donation | 1.4c (−0.3%) | –8.2 (1.7%) | –11.3 (2.2%) |
| ΔEorb(rest)e | –13.2 (2.4%) | –16.2 (3.3%) | –20.9 (4.1%) | |
| [Hf(CO)6]2– | ||||
| Hf2– (S) + (CO)6 (S) | ||||
| ΔEint | –490.4 | |||
| ΔEmetahybrid | 39.3 | |||
| ΔEPauli | 317.2 | |||
| ΔEelstatd | –343.0 (40.5%) | |||
| ΔEorbd | –503.9 (59.5%) | |||
| ΔEorb(1)(t2g)e | [M(d)] → (CO)6 π-backdonation | –373.9 (74.2%) | ||
| ΔEorb(2) (eg)e | [M(d)] ← (CO)6 σ-donation | –82.8 (16.4%) | ||
| ΔEorb(3) (a1g)e | [M(s)] ← (CO)6 σ-donation | –11.0 (2.2%) | ||
| ΔEorb(4) (t1u)e | [M(p)] ← (CO)6 σ-donation | –9.9 (2.0%) | ||
| ΔEorb(rest)e | –26.3 (5.2%) | |||
| [M(CO)8]− | ||||
| Sc– (S) + (CO)8 (S) | Y– (S) + (CO)8 (S) | La– (S) + (CO)8 (S) | ||
| ΔEint | –438.3 | –346.4 | –279.9 | |
| ΔEmetahybrid | 21.2 | 38.9 | 43.5 | |
| ΔEPauli | 140.0 | 169.8 | 154.6 | |
| ΔEelstatd | –200.0 (33.3%) | –199.1 (35.9%) | –175.0 (36.6%) | |
| ΔEorbd | –399.8 (66.7%) | –356.0 (64.1%) | –303.0 (63.4%) | |
| ΔEorb(1) (eg)e | [M(d)] → (CO)8 π-backdonation | –332.1 (83.1%) | –267.5 (75.1%) | –224.2 (74.0%) |
| ΔEorb(2) (t2g)e | [M(d)] ← (CO)8 σ-donation | –48.9 (12.2%) | –59.3 (16.7%) | –48.3 (15.9%) |
| ΔEorb(3) (a1g)e | [M(s)] ← (CO)8 σ-donation | –2.0 (0.5%) | –4.7 (1.3%) | –3.5 (1.2%) |
| ΔEorb(4) (t1u)e | [M(p)] ← (CO)8 σ-donation | –2.4 (0.6%) | –6.1 (1.7%) | –5.2 (1.7%) |
| ΔEorb(rest)e | –14.4 (3.6%) | –18.4 (5.2%) | –21.8 (7.2%) | |
| M(CO)2 | ||||
| Ca (S) + (CO)2 (S) | Sr (S) + (CO)2 (S) | Ba (S) + (CO)2 (S) | ||
| ΔEint | –151.3 | –147.6 | –67.0 | |
| ΔEmetahybrid | 12.3 | 10.7 | 17.1 | |
| ΔEPauli | 50.1 | 46.2 | 44.0 | |
| ΔEelstatd | –44.9 (21.0%) | –38.4 (18.8%) | –40.2 (31.4%) | |
| ΔEorbd | –168.8 (79.0%) | –166.0 (81.2%) | –87.9 (68.6%) | |
| ΔEorb(1)e | [M(d)] → (CO)2 π-backdonation | –150.6 (89.2%) | –150.5 (90.7%) | –66.0 (75.1%) |
| ΔEorb(2)e | [M(d)] ← (CO)2 σ-donation | –11.4 (6.8%) | –10.0 (6.0%) | –12.5 (14.2%) |
| ΔEorb(3)e | [M(p)] ← (CO)2 σ-donation | –1.6 (0.9%) | –0.8 (0.5%) | –2.9 (3.3%) |
| ΔEorb(rest)e | –5.2 (3.1%) | –4.7 (2.8%) | –6.5 (7.4%) | |
| Ca+ (D) + (CO)−2 (D) | Sr+ (D) + (CO)−2(D) | Ba+ (D) + (CO)−2 (D) | ||
| ΔEint | –188.2 | –185.0 | –161.2 | |
| ΔEmetahybrid | 0.8 | 1.7 | 5.8 | |
| ΔEPauli | 62.9 | 56.8 | 50.6 | |
| ΔEelstatd | –169.7 (67.4%) | –159.1 (65.3%) | –149.9 (68.9%) | |
| ΔEorbd | –82.1 (32.6%) | –84.4 (34.7%) | –67.6 (31.1%) | |
| ΔEorb(1)e | [M(d)] → (CO)2 π-backdonation | –55.3 (67.4%) | –60.7 (71.9%) | –43.7 (64.6%) |
| ΔEorb(2)e | [M(d)] ← (CO)2 σ-donation | –15.5 (18.9%) | –13.9 16.5%) | –14.1 (20.9%) |
| ΔEorb(3)e | [M(p)] ← (CO)2 σ-donation | –3.5 (4.3%) | –2.7 (3.2%) | –3.2 (4.7%) |
| ΔEorb(rest)e | –7.8 (9.5%) | –7.1 (8.4%) | –6.6 (9.8%) | |
| [Ba(CO)]•+ | ||||
| Ba+ (D) + (CO) (S) | ||||
| ΔEint | –21.2 | |||
| ΔEmetahybrid | 7.4 | |||
| ΔEPauli | 32.0 | |||
| ΔEelstatd | –22.2 (36.6%) | |||
| ΔEorbd | –38.4 (63.4%) | |||
| ΔEorb(1)e | [M(d)] → (CO) π-backdonation | –20.3 (52.9%) | ||
| ΔEorb(2)e | [M(d)] ← (CO) σ-donation | –13.2 (34.4%) | ||
| ΔEorb(rest)e | –4.9 (12.8%) | |||
a
Results of the neutral alkaline earth dicarbonyls M(CO)2 using neutral and charged fragments in their singlet (S) or doublet (D) states. All energy values are given in kcal/mol.
b
The symmetry notations σ and π refer to the orbitals of the CO ligand and not to the symmetry of the complex.
c
The small positive value is due to a polarization of the orbital charge.
d
The values in parentheses give the percentage contribution to the total attractive interactions ΔEelstat + ΔEorb.
e
The values in parentheses give the percentage contribution to the total orbital interactions ΔEorb.