Table 1.
X-ray structural parameters determining acetate binding mode in Co/Ni complexes
| Complex | Mn+ | r (pm)36 | Nax–M–Nax angle (°) | Neq–M–Neq angle (°) | O–M–O angle (°) | OAc binding mode | M–N bond distance (Å) | M–O bond distance (Å) |
|---|---|---|---|---|---|---|---|---|
| [Co2(OAc)]2+ | Co3+ | 69 | 170.77(16) | 90.42(17) | 68.16(18) | Iso-bidentate | Co–Nax = 2.033(3) Co–Neq = 1.898(3) |
Co–O = 1.939(3) |
| [Co6(OAc)]2+ | Co3+ | 69 | 171.06(19) | 90.85(19) | 67.57(19) | Iso-bidentate | Co–Nax = 2.006 (avg) Co–Neq = 1.903 (avg) |
Co–O = 1.933 (avg) |
| [Co5(OAc)(H2O)]+ | Co2+ | 89 | 173.0(2) | 83.39(19) | 88.18(18) | Monodentate/H2O | Co–Nax = 2.179 (avg) Co–Neq = 2.126 (avg) |
Co–O = 2.042(4) (OAc) Co–O = 2.111(5) (H2O) |
| 19[Ni5(OAc)(H2O)]+ | Ni2+ | 83 | 173.41(11) | 84.02(10) | 88.35(10) | Monodentate/H2O | Ni–Nax = 2.192 (avg) Ni–Neq = 2.097 (avg) |
Ni–O = 2.064(2) (OAc) Ni–O = 2.077(3) (H2O) |
| 19[Ni1(OAc)(H2O)]+ | Ni2+ | 83 | 175.41(10) | 85.50(12) | 88.18(11) | Monodentate/H2O | Ni–Nax = 2.183 (avg) Ni–Neq = 2.132 (avg) |
Ni–O = 2.052(2) (OAc) Ni–O = 2.109(3) (H2O) |
| [Ni2(OAc)(H2O)]+ | Ni2+ | 83 | 163.52(6) | 85.59(7) | 87.61(6) | Monodentate/H2O | Ni–Nax = 2.1532 (avg) Ni–Neq = 2.0580 (avg) |
Ni–O = 2.0639(14) (OAc) Ni–O = 2.0770(15) (H2O) |
| [Ni4(OAc)]+ | Ni2+ | 83 | 163.71(13) | 87.69(14) | 63.01(12) | Iso-bidentate | Ni–Nax = 2.150 (avg) Ni–Neq = 2.025 (avg) |
Ni–O = 2.106 (avg) |
| [Ni6(OAc)]+ | Ni2+ | 83 | 163.82(14) | 87.08(14) | 62.78(13) | Iso-bidentate | Ni–Nax = 2.145 (avg) Ni–Neq = 2.023 (avg) |
Ni–O = 2.094 (avg) |
| 37[Co(Bn2Cyclam)(OAc)]+ | Co2+ | 89 | 171.54(10) | 97.16(11) | 61.51(9) | Iso-bidentate | Co–Nax = 2.254 (avg) Co–Neq = 2.107 (avg) |
Co–O = 2.134 (avg) |
| 37[Ni(Bn2Cyclen)(OAc)]+ | Ni2+ | 83 | 160.84(9) | 101.83(10) | 62.31(8) | Iso-bidentate | Ni–Nax = 2.180 (avg) Ni–Neq = 2.033 (avg) |
Ni–O = 2.115 (avg) |
| 37[Ni(Bn2Cyclen)(OAc)(H2O)]+ | Ni2+ | 83 | 160.29(7) | 96.99(7) | 88.19(6) | Monodentate/H2O | Ni–Nax = 2.161 (avg) Ni–Neq = 2.066 (avg) |
Ni–O = 2.0525(15) (OAc) Ni–O = 2.0750(15) (H2O) |
| 38[Ni(Me4Cyclen)(OAc)]+FODTAV | Ni2+ | 83 | 158.44(16) | 108.64(17) | 61.92(14) | Iso-bidentate | Ni–Nax = 2.154 (avg) Ni–Neq = 2.104 (avg) |
Ni–O = 2.114 (avg) |
| 39[Ni(Cyclen)(OAc)]+XADMAR | Ni2+ | 83 | 160.5(2) | 102.1(2) | 61.47(15) | Iso-bidentate | Ni–Nax = 2.098(4) Ni–Neq = 2.050 (avg) |
Ni–O = 2.121 (avg) |
| 40[Ni(Bn1Cyclam)(OAc)]+NEXQEN | Ni2+ | 83 | 173.54(6) | 100.36(6) | 62.01(6) | Iso-bidentate | Ni–Nax = 2.149 (avg) Ni–Neq = 2.073 (avg) |
Ni–O = 2.133 (avg) |