Coexistence of Three Different Spin States in a Cyanido-Bridged Trinuclear Iron(III) Complex with an Unusual FeIII to Ligand Charge Transfer.
Chemistry
; 29(30): e202300100, 2023 May 26.
Article
em En
| MEDLINE
| ID: mdl-36929941
We report a trinuclear iron(III) cyanido-bridged complex trans-[CpMe3 FeIII (dppe)(CN)]2 [FeIII (LN4 )][PF6 ]4 (2[PF6 ]4 ) as the oxidation product of binuclear complex [CpMe3 (dppe)FeII CN-FeIII (LN4 )][PF6 ] (1[PF6 ]) (CpMe3 =1, 2, 4-trimethyl-1,3-cyclo-pentadienyl, dppe=1,2-bis(diphenylphosphino)ethane, LN4 =pentane-2,4-dione-bis(S-methylisothiosemicarbazonato). Complex 1[PF6 ] possesses an intermediate-spin five-coordinated FeIII (S=3/2) which couples antiferromagnetically to the π-radical ligand (Lâ
N4 )2- and shows a LMCT (ligand to metal charge transfer) transition from (Lâ
N4 )2- to FeIII and the FeII âFeIII MMCT transition. Upon oxidation of 1[PF6 ], (Lâ
N4 )2- loses one electron to be the strong electron-attracting ligand (LOx N4 )- and the intermediate-spin five-coordinated FeIII (S=3/2) becomes a low-spin six-coordinated FeIII (S=1/2) in 2[PF6 ]4 . Also interestingly, 2[PF6 ]4 presents the coexistence of three different spin states (one S=3/2 and two S=1/2) and an uncommon FeIII â(LOx N4 )- MLCT transition, confirmed by the experimental results and supported by the TDDFT calculations.
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MEDLINE
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Ano de publicação:
2023
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Article