Table 2. Experimental and Computed Parameters to Estimate the Photomodulation of the Properties of the Phosphine Ligands DTE-COCF3, DTE-C6F5, and DTE-Ph.
| free
ligands |
PdII complexesa | |||
|---|---|---|---|---|
| Δc–o(1JP,Se) [Hz]b | Δc–o(qMullikenP)c,d | Δc–o(%sP)c,e | Δc–o(BEP–Pd) [kcal·mol–1]c,f | |
| DTE-COCF3 | 14 | 0.014 | 0.79 | –1.98 |
| DTE-C6F5 | 7 | 0.004 | 0.42 | –0.92 |
| DTE-Ph | 5 | <0.001 | 0.34 | –0.64 |
a
trans-[PdCl2(DTE-COCF3)2], trans-[PdCl2(DTE-C6F5)2], and trans-[PdCl2(DTE-Ph)2].
b
Difference in 1JP,Se for the corresponding selenides measured in CDCl3.
c
Computed at the B3LYP-D3 level in THF (see the Experimental Section for further details).
d
Difference in Mulliken charges in electronic units on the phosphorus atom.
e
Difference in percentage of s character of the phosphorus lone pair of electrons.
f
Difference in phosphine-PdII bond energy (per one bond) between the oo and cc isomers.