Table 3 NBO second-order perturbation stabilization energies for the dominant non-Lewis interactions, and the orbital interaction energies ΔEorb for the dominant bonding interactions shown in Fig. 2a

From: Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding

 

aNBO ΔE(2)

bETS-NOCV

 

Stabilization interactions

ΔEorb

Compound

c1

c2

c3

d4

d5

σ2

π

σ1

\({[{{{{{{{{\rm{OU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{-}{{{{{{{\rm{O}}}}}}}}]}^{2+}\) D∞h

2.2

14.2

1.8

29.8

29.8

−320.9

−168.6

−16.6

\({[{{{{{{{{\rm{OU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{-}{{{{{{{\rm{O}}}}}}}}]}^{2+}\) C2v

0.8

7.9

1.6

21.0

21.0

−288.9

−164.7

−14.0

OUVI−C

2.1

11.7

2.4

79.7

42.9

−473.0

−317.2

−24.6

\({({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NTh}}}}}}}}}^{{{{{{{{\rm{IV}}}}}}}}}{-}{{{{{{{\rm{Cl}}}}}}}}\)

0.0

0.0

0.0

11.6

28.2

−26.6

−10.7

0.0

\({[{({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NTh}}}}}}}}}^{{{{{{{{\rm{IV}}}}}}}}}{-}{{{{{{{\rm{N}}}}}}}}]}^{2-}\)

1.0

7.1

1.1

82.4

13.8

−186.1

−101.8

−34.6

\({({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{-}{{{{{{{\rm{N}}}}}}}}\)

1.1

11.3

0.6

128.9

28.9

−287.1

−153.2

−28.3

\({[{({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NU}}}}}}}}}^{{{{{{{{\rm{V}}}}}}}}}{-}{{{{{{{\rm{N}}}}}}}}]}^{1-}\)

0.4

8.0

0.4

112.1

19.6

−237.0

−120.2

−30.0

\({[{({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NU}}}}}}}}}^{{{{{{{{\rm{IV}}}}}}}}}{-}{{{{{{{\rm{N}}}}}}}}]}^{2-}\)

0.8

7.3

0.7

73.5

24.5

−169.4

−83.4

−27.1

\({({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NU}}}}}}}}}^{{{{{{{{\rm{V}}}}}}}}}{-}{{{{{{{\rm{O}}}}}}}}\)

0.0

6.0

0.0

79.8

22.6

−144.7

−70.2

−19.6

\({({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NNp}}}}}}}}}^{{{{{{{{\rm{V}}}}}}}}}{-}{{{{{{{\rm{O}}}}}}}}\)

0.3

7.6

0.0

85.6

30.0

−172.7

−48.4

−17.4

\({{{{{{{{\rm{MeU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{b}}}}}}}}})}_{3}{-}{{{{{{{\rm{O}}}}}}}}\)

0.8

10.3

0.6

62.9

61.3

−179.3

−87.6

−19.6

\({{{{{{{{\rm{PhCCU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{b}}}}}}}}})}_{3}{-}{{{{{{{\rm{O}}}}}}}}\)

0.6

7.3

0.0

47.3

90.4

−166.8

−89.3

−16.7

CUVI−Oe

1.4

9.9

0.0

42.9

79.7

−209.1

−77.9

−13.7

\({{{{{{{\rm{O}}}}}}}}{({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{b}}}}}}}}})}_{3}{{{{{{{{\rm{U}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{-}{{{{{{{{\rm{Me}}}}}}}}}^{e}\)

0.0

0.0

0.0

61.3

62.9

−82.6

−9.1

–

\({({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{-}{{{{{{{{\rm{N}}}}}}}}}^{{{{{{{{\rm{f}}}}}}}}}\)

1.2

10.3

0.6

81.0

21.2

−287.0

−152.6

−27.9

  1. DFT/B3LYP calculations.
  2. a,bEnergies in kcal mol−1.
  3. c,d Interactions illustrated in Fig. 2.
  4. a NBO second-order perturbation theory donor–acceptor ΔE(2) stabilization energy.
  5. b ETS-NOCV contributions to ΔEorb. The ΔEorb and ΔE(2) for the two π-bonding interactions are equivalent and only one is listed.
  6. cΔE(2) donor–acceptor interactions involving 6s and 6p An semi-core shells.
  7. dΔE(2) donor–interaction between the terminal and trans ligand lone pair and formally unoccupied An-centered NBOs. For the symmetric small compounds interactions nos. 4 and 5 are identical.
  8. eData for the trans–An bond for a selected compounds.
  9. fData for the full experimental \({({{{{{{{{\rm{R}}}}}}}}}^{{{{{{{{\rm{a}}}}}}}}})}_{3}{{{{{{{{\rm{NU}}}}}}}}}^{{{{{{{{\rm{VI}}}}}}}}}{{{{{{{\rm{N}}}}}}}}\) structure for comparison.
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