Table 2. Selected Bond Lengths (Å), Bond Angles (°), and Torsion Angles (°) of Complexes 1–3a.
| complex | geometry | XRD | B3PBE (SGS) | B3PBE (LLTS) |
|---|---|---|---|---|
| 1 | bond lengths | |||
| Re1-O(OOC) | 2.160(8) | 2.15 | 2.15 | |
| Re1-N(phen) | 2.160(11), 2.173(10) | 2.20 | 2.20 | |
| Re1-C(COAx) | 1.946(17) | 1.91 | 1.91 | |
| Re1-C(COPl) | 1.919(15) | 1.92 | 1.92 | |
| Re2-N(py) | 2.219(8) | 2.24 | 2.21 | |
| Re2-C2(COAx) | 1.950(12) | 1.92 | 1.97 | |
| Re2-C1(COPl) | 1.936(14), 1.926(14) | 1.92 | 1.94, 2.00 | |
| Re2-N(phen) | 2.180(10), 2.181(10) | 2.20 | 2.06, 2.18 | |
| Re1-Re2 distance | 9.26 | 9.33 | 9.30 | |
| angles | ||||
| N-Re1-N(phen) | 76.3(4) | 75.1 | 75.1 | |
| C(COAx)-Re1-O(OOC) | 179.4(6) | 174.2 | 174.2 | |
| N-Re2-N(phen) | 75.5(4) | 75.1 | 77.2 | |
| C(COAx)-Re2-N(py) | 176.3(5) | 178.3 | 177.4 | |
| N(phen)-Re1-O(OOC) | 79.2(3), 83.0(4) | 80.0, 83.2 | 80.0, 83.2 | |
| N(phen)-R2-N(py) | 82.3(4), 86.1(3) | 85.2, 85.3 | 84.8, 89.7 | |
| torsion angles | ||||
| Re1-N(phen)-C(COPl)-C(COPl) | 179.4(11), 178.5(10) | 178.1 | 178.7 | |
| Re2-N(phen)-C(COPl)-C(COPl) | 177.2(11), 177.6(9) | 178.3 | 179.5 | |
| 2 | bond lengths | |||
| Re-N(py) | 2.2207(19) | 2.24 | 2.22 | |
| Re-N(phen) | 2.1809(19), 2.1769(19) | 2.20 | 2.06, 2.18 | |
| Re-C(COAx) | 1.913(2) | 1.92 | 1.96 | |
| Re-C(COPl) | 1.920(3), 1.935(3) | 1.92 | 1.94, 2.00 | |
| angles | ||||
| N-Re-N(phen) | 76.08(7) | 75.2 | 77.2 | |
| C(COAx)-Re-N(py) | 177.22(8) | 178.4 | 177.9 | |
| torsion angle | ||||
| Re-N(phen)-C(COPl)-C(COPl) | 178.00 | 178.9 | 178.0 | |
| 3 | bond lengths | |||
| Re-O(OOC) | 2.1342(17) | 2.13 | 2.03 | |
| Re-N(phen) | 2.175(2), 2.1685(19) | 2.20 | 2.10, 2.17 | |
| Re-C(COAx) | 1.908(3) | 1.91 | 1.98 | |
| Re-C(COPl) | 1.924(3), 1.912(3) | 1.92 | 1.94, 1.99 | |
| angles | ||||
| N-Re-N(phen) | 75.60(7) | 75.0 | 77.3 | |
| C(COAx)-Re-O(OOC) | 176.51(16) | 173.3 | 171.9 | |
| torsion | ||||
| Re-N(phen)-C(COPl)-C(COPl) | 177.9 | 177.4 | 177.9 |
a
In complex 1, the Re atom coordinated to O(OOC) is labeled as Re1 and the Re atom coordinated to N(py) is labeled as Re2. (SGS = singlet ground state; LLTS = lowest-lying triplet state; phen = 1,10-phenanthroline; py = pyridine; COAx = CO perpendicular to phen; COPl = CO co-planar with phen.)