Table 1 Results of EDA-NOCV calculations for singlet state [OB-M©B7O7-BO]− complexes at the PBE0/TZ2P level using neutral M atoms in the quintet reference state with ns0np1(n − 1)d7 electron configuration and [OB-B7O7-BO]− (L, quintet) as interacting fragments.
Energy terms | Number of orbitals | Assignments | Interaction energies for M (quintet, ns0np1(n − 1)d7) + [OB-B7O7-BO]− (L, quintet) | ||
|---|---|---|---|---|---|
M = Fe | M = Ru | M = Os | |||
∆Eint | −535.7 | −591.3 | −687.0 | ||
∆EPauli | 518.9 | 746.5 | 1071.3 | ||
∆EAttr | −1054.6 | −1337.8 | −1758.3 | ||
∆Eelstat[a] | −592.6 (56.2%) | −760.0 (56.8%) | −953.9 (54.3%) | ||
∆Eorb[a] | −462.0 (43.8%) | −577.8 (43.2%) | −804.4 (45.7%) | ||
∆Eorb(1)[b] (A1′) | 1 | L-M(dz2) electron-sharing bonds | −97.6 (21.1%) | −128.2 (22.2%) | −305.5 (38.0%) |
∆Eorb(2)[b] (E2′) | 2 | L-M(dxy/dx2–y2) electron-sharing bonds | −195.6 (42.3%) | −274.4 (47.5%) | −280.4 (34.9%) |
∆Eorb(3)[b] (E1″) | 1 | L-M(pz) electron-sharing bonds | −46.7 (10.1%) | −50.3 (8.7%) | −53.8 (6.7%) |
∆Eorb(4)[b] (A2″) | 2 | L ← M(dxz/dyz) backdonation | −94.0 (20.3%) | −90.2 (15.6%) | −123.6 (15.4%) |
∆Eorb(5)[b] (E1′) | 2 | L → M(px/py) donation | −15.4 (3.3%) | −15.8 (2.7%) | −16.8 (2.1%) |
∆Eorb(6)[b] (A1′) | 1 | L → M(s) donation | −4.8 (1.0%) | −7.6 (1.3%) | −12.0 (1.5%) |
∆Erest[b] | −7.9 (1.7%) | −11.3 (2.0%) | −12.3 (1.5%) | ||
