Table 6. EDA-NOCV Results for Complexes W-XY (X = Ge, Sn, Pb; Y = B–Tl) Using the Moieties [W(CO)5] and [XY(Cp*)2] as Interacting Fragments at the BP86/TZ2P+// BP86/def2-SVP Levela.
| complex | ΔEintb | ΔEPauli | ΔEelstatc | ΔEorbd | ΔEσe | ΔEπe | ΔEreste | ΔEprep | ΔE (= −De) |
|---|---|---|---|---|---|---|---|---|---|
| [(YCp*)2X → W(CO)5] = (YCp*)2X + W(CO)5 | |||||||||
| W-GeB | –64.4 | 115.2 | –108.2 (60.2%) | –71.5 (39.8%) | –62.6 (87.6%) | –7.9 (11.0%) | –1.0 (1.4%) | 19.8 | –44.6 (−44.4)f |
| W-GeAl | –51.2 | 102.3 | –90.7 (59.1%) | –62.8 (40.9%) | –51.9 (82.6%) | –8.6 (13.7%) | –2.3 (3.7%) | 3.6 | –47.6 (−45.5)f |
| W-GeGa | –55.1 | 117.2 | –103.0 (59.8%) | –69.2 (40.2%) | –56.4 (81.5%) | –10.8 (15.6%) | –2.0 (2.9%) | 3.2 | –51.9 (−48.9)f |
| W-GeIn | –57.2 | 127.4 | –110.2 (59.7%) | –74.3 (40.3%) | –59.0 (79.4%) | –13.4 (18.0%) | –1.9 (2.6%) | 4.9 | –52.3 (−50.0)f |
| W-GeTl | –74.1 | 170.8 | –153.4 (62.6%) | –91.6 (37.4%) | –66.9 (73.0%) | –22.7 (24.8%) | –2.0 (2.2%) | 19.4 | –54.7 (−53.6)f |
| W-SnB | –66.5 | 120.2 | –112.8 (60.4%) | –73.9 (39.6%) | –63.7 (86.2%) | –9.1 (12.3%) | –1.1 (1.5%) | 17.2 | –49.3 (−49.0)f |
| W-SnAl | –53.0 | 109.1 | –95.5 (58.9%) | –66.7 (41.1%) | –56.6 (84.9%) | –7.9 (11.8%) | –2.2 (3.3%) | 5.6 | –47.4 (−46.7)f |
| W-SnGa | –56.3 | 119.6 | –105.9 (60.2%) | –69.9 (39.8%) | –59.5 (85.1%) | –8.6 (12.3%) | –1.8 (2.6%) | 5.8 | –50.5 (−49.5)f |
| W-SnIn | –56.7 | 123.3 | –108.2 (60.1%) | –71.9 (39.9%) | –59.9 (83.3%) | –9.3 (12.9%) | –1.7 (2.8%) | 5.7 | –51.0 (−49.9)f |
| W-SnTl | –67.1 | 144.3 | –130.5 (61.7%) | –80.9 (38.3%) | –65.3 (80.7%) | –12.9 (15.9%) | –2.7 (3.4%) | 12.9 | –54.2 (−53.9)f |
| W-PbB | –67.9 | 117.5 | –108.2 (58.3%) | –77.3 (41.7%) | –69.4 (89.8%) | –6.7 (8.7%) | –1.2 (1.5%) | 17.0 | –50.9 (−50.5)f |
| W-PbAl | –53.5 | 109.2 | –94.8 (58.2%) | –68.0 (41.8%) | –58.2 (85.6%) | –7.9 (11.6%) | –1.9 (2.8%) | 6.3 | –47.2 (−46.2)f |
| W-PbGa | –56.4 | 115.9 | –102.7 (59.6%) | –69.6 (40.4%) | –60.0 (86.2%) | –8.2 (11.8%) | –1.4 (2.0%) | 5.8 | –50.6 (−49.9)f |
| W-PbIn | –55.9 | 117.8 | –103.3 (59.5%) | –70.4 (40.5%) | –60.7 (86.2%) | –8.7 (12.4%) | –1.0 (1.4%) | 4.8 | –51.1 (−49.6)f |
| W-PbTl | –66.2 | 135.0 | –121.6 (60.4%) | –79.6 (39.6%) | –65.8 (82.7%) | –12.0 (15.1%) | –1.8 (2.2%) | 11.9 | –54.3 (−52.8)f |
a
The complexes were analyzed under C1 symmetry. Energy values are in kcal mol–1.
b
The total instantaneous interaction energy, ΔEint = ΔEPauli + ΔEelstat + ΔEorb.
c
The values in parentheses are the percentage contributions to the total attractive interaction, ΔEelstat + ΔEorb.
d
The values in parentheses are the percentage contributions to the total attractive interaction, ΔEelstat + ΔEorb.
e
The values in parentheses are the percentage contributions to the total orbital interaction ΔEorb = ΔEσ + ΔEπ + ΔErest.
f
The values in parentheses give the bond dissociation energy, De, at the BP86/def2-TZVPP//BP86/def2-SVP level of theory.