Table 3. Optimized Pd–S, C–C, and C–S Bond Lengths (d, Å) and Wiberg Bond Indices (WBI) within the 1,2-Dithiolene Ligands L and L′ of [Pd(L)(L′)]₂^q– Complexes (L = L′ = Me₂timdt for 1^q–; L = Me₂timdt, L′ = mnt for 3^q–; L = L′ = mnt for 4^q–; q = 0, 1, 2)^a.

			L						L′
	GS	symmb	dPd–S	dC–C	dC–S	WBIC–C	WBIC–S	dPd–S	dC–C	dC–S	ΔdC–Cc	WBIC–C	WBIC–S
1	triplet	3B1u	2.351	1.410	1.698	1.177	1.378
	singlet	1Ag	2.314	1.404	1.697	1.269	1.276
	BS		2.307	1.401	1.699	1.251	1.274
[Pd(Et2timdt)2] (structural data)d,e			2.295(2)	1.397(9)	1.689(8)
1–	doublet	2B2g	2.337	1.381	1.717	1.385	1.192
12–	singlet	1Ag	2.376	1.365	1.739	1.482	1.126
3	triplet	3B1	2.359	1.408	1.700	1.226	1.267	2.305	1.404	1.701	0.004	1.307	1.098
	singlet	1B1	2.342	1.428	1.674	1.168	1.397	2.263	1.393	1.725	0.035	1.417	1.098
	BS	–	2.344	1.422	1.682	1.186	1.354	2.273	1.389	1.717	0.033	1.384	1.098
3 (structural data)f			2.314(2)	1.454(16)	1.660(8)			2.258(2)	1.364(16)	1.724(8)	0.090
3–	doublet	2A1	2.369	1.397	1.697	1.290	1.276	2.286	1.376	1.740	0.021	1.451	1.138
32–	singlet	1B1	2.384	1.364	1.737	1.477	1.131	2.323	1.381	1.744	–0.017	1.424	1.130
4	triplet	3B1u	2.325	1.410	1.696	1.277	1.329
	singlet	1Ag	2.275	1.403	1.701	1.325	1.305
	BS		2.289	1.451	1.699	1.311	1.312
4–	doublet	2B2g	2.295	1.386	1.725	1.405	1.195
42–	singlet	1Ag	2.332	1.380	1.743	1.428	1.131
4 (structural data)e,g			2.263(7)	1.39(2)	1.71(1)

^aFor neutral species (q = 0), the distances in the open-shell paramagnetic triplet, CS diamagnetic singlet, and singlet diradical (BS) configurations are reported.

^bGS-symmetry representations are referenced to the D_2h (1, 4) and C_2v (3) point groups, with the complex molecule laying on the yz plane and the main axis being coincident with z.

^cΔd_C–C = difference in d_C–C values calculated within the two ligands Me₂timdt^–q/2–1 and mnt^–q/2–1 in 3^q–.

^dReference (45).

^eAverage value.

^fThis work.

^gIsolated in (perylene)₂(4). Reference (116).