Diaqua-2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12,3,1]octadeca-1(18),2,12,14,16-pentaeneiron(II) chloride perchlorate

Drew, Michael G. B.; Othman, Abdul Hamid; Mcilroy, P. D. A.; Nelson, S. M.

doi:10.1107/s0567740876004597

Cited by 21 publications

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“…A search of the CSD found a Fe(II) complex of 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12,3,1]octadeca-1(18),2,12,14,16-pentaene (PABODP) (CSD refcode AMZOFE) that looked interesting . With axial PF 3 groups, Δ E HL for [Mn(PABODP)(PF 3 ) 2 ] 3+ is predicted to be 6.6 kcal mol –1 while Δ E IL is 55.8 kcal mol –1 (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…A search of the CSD found a Fe(II) complex of 2,13dimethyl-3,6,9,12,18-pentaazabicyclo [12,3,1]octadeca-1(18),2,12,14,16-pentaene (PABODP) (CSD refcode AM-ZOFE) that looked interesting. 72 With axial PF 3 groups, ΔE HL for [Mn(PABODP)(PF 3 ) 2 ] 3+ is predicted to be 6.6 kcal mol −1 while ΔE IL is 55.8 kcal mol −1 (Figure 12). However, in contrast to the POPY analogue, the Mn−P HS bond lengths are much shorter at 2.366 Å and the electronic binding energy for dissociating one PF 3 group is substantially larger at about 17 kcal mol −1 .…”

Section: Inorganic Chemistrymentioning

confidence: 99%

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DFT Analysis of Spin Crossover in Mn(III) Complexes: Is a Two-Electron S = 2 to S = 0 Spin Transition Feasible?

Amabilino

Deeth

2017

Inorg. Chem.

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Six-coordinate, rigorously octahedral d Mn(III) spin crossover (SCO) complexes are limited by symmetry to an S = 1 (intermediate spin, IS) to S = 2 (high spin, HS) transition. In order to realize the potential S = 0 to S = 2 transition, a lower symmetry and/or change in coordination number is needed, which we explore here computationally. First, a number of complexes are analyzed to develop a reliable and relatively fast DFT protocol for reproducing known Mn(III) spin state energetics. The hybrid meta-GGA functional TPSSh with a modest split valence plus polarization basis set and an empirical dispersion correction is found to predict correctly the ground spin state of Mn(III) complexes, including true low-spin (LS) S = 0 systems, with a range of donor sets including the hexadentate [NO] Schiff base ligands. The electronic structure design criteria necessary for realizing a ΔS = 2 SCO transition are described, and a number of model complexes are screened for potential SCO behavior. Five-coordinate trigonal-bipyramidal symmetry fails to yield any suitable systems. Seven-coordinate, approximately pentagonal bipyramidal symmetry is more favorable, and when a known pentadentate macrocyclic donor is combined with π-acceptor axial ligands, a novel Mn(III) complex, [Mn(PABODP)(PF)] (PABODP = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene), is predicted to have the right spin state energetics for an S = 0 to S = 2 transition. Successful synthesis of such a complex could provide the first example of a ΔS = 2 SCO transition for d Mn(III). However, the combination of a rigid macrocycle and a high coordination number dilutes the stereochemical activity of the d electrons, leading to relatively small structural changes between HS and LS systems. It may therefore remain a challenge to realize strong cooperative effects in Mn(III) systems.

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Section: Resultsmentioning

confidence: 99%

Section: Inorganic Chemistrymentioning

confidence: 99%

DFT Analysis of Spin Crossover in Mn(III) Complexes: Is a Two-Electron S = 2 to S = 0 Spin Transition Feasible?

Amabilino

Deeth

2017

Inorg. Chem.

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“…A similar manganese(II) complex has been isolated as a perchlorate salt . Complexes with coordination numbers exceeding 6 are uncommon for iron(II) and have generally been obtained with ligands having donor sets formed by nitrogen and oxygen atoms. , As far as we are aware, only four other eight-coordinate iron(II) complexes, in which all the donor nitrogens are part of chelating organic ligands, have been characterized structurally …”

Section: Resultsmentioning

confidence: 99%

Iron(II) Polyamine Chemistry: Variation of Spin State and Coordination Number in Solid State and Solution with Iron(II) Tris(2-pyridylmethyl)amine Complexes

1998

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The synthetic system of Fe(SO 3 CF 3 ) 2 and one or two TPA ligands (TPA ) tris(2-pyridylmethyl)amine) affords a series of complexes that demonstrate the complexities of the solid-state and solution coordination chemistry of labile iron(II) even with a multidentate ligand. The low-spin [Fe(TPA)(CH 3 CN) 2 ](SO 3 CF 3 ) 2 (1-OTf) complex forms in acetonitrile, but the high-spin complex Fe(TPA)(SO 3 CF 3 ) 2 (2) forms in chloroform. The methanolbound complex [Fe(TPA)(CH 3 OH) 2 ](BPh 4 ) 2 (3) forms in the presence of the noncoordinating anion, BPh 4 -, and six-coordinate [Fe(TPA) 2 ](SO 3 CF 3 ) 2 (4-OTf) and eight-coordinate [Fe(TPA) 2 ](BPh 4 ) 2 (4-BPh 4 ) form in the presence of excess ligand. Their behavior in solution is explored by studying their magnetic properties and NMR spectra, which indicate the presence of spin and coordination equilibria. The crystal structures of these complexes are reported. Crystallographic parameters are as follows. 1-OTf‚CH 3 CN: C 26 H 27 F 6 FeN 7 O 6 S 2 , monoclinic, P2 1 /n, a ) 12.418(2) Å, b ) 16.192(4) Å, c ) 15.855(2) Å, β ) 92.09(2)°, Z ) 4. 2: C 20 H 18 F 6 FeN 4 O 6 S 2 , monoclinic, P2 1 /c, a ) 17.636(2) Å, b ) 9.659(1) Å, c ) 16.004(2) Å, β ) 113.29 (1)°, Z ) 4. 3‚CH 3 OH: C 69 H 70 B 2 -FeN 4 O 3 , monoclinic, P2 1 /n, a ) 17.525(1) Å, b ) 19.150(2) Å, c ) 17.703(1) Å, β ) 100.36(1)°, Z ) 4. 4-OTf: C 38 H 36 F 6 FeN 8 O 6 S 2 , monoclinic, Pc, a ) 10.236(1) Å, b ) 10.129(1) Å, c ) 19.251(1) Å, β ) 92.27(1)°, Z ) 2. 4-BPh 4 : C 84 H 76 B 2 FeN 8 , monoclinic, P2 1 /n, a ) 12.489(1) Å, b ) 14.189(1) Å, c ) 19.843(1) Å, β ) 102.84-(1)°, Z ) 2.

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“…The crystal structures of three PBP Fe(II) complexes18, 19 and four PBP Fe(III)5,20,24 complexes have been reported in the literature. In the Fe(DAPSC)(Cl)(H20)+ cation the axial Fe-Cl bond of 2.507 (2) Á is longer than in the FeCl2-(DAPSC)+ complex, 2.344 Á, by slightly more than the change in the ionic radius.…”

Section: Methodsmentioning

confidence: 99%

Pentagonal-bipyramidal complexes. Crystal and molecular structures of chloroaqua(2,6-diacetylpyridine bis(semicarbazone))manganese(II), -iron(II), -cobalt(II), and -zinc(II) chloride dihydrates

Palenik¹,

Wester²

1978

Inorg. Chem.

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The crystal structure of the dioxygen adduct of [Fe(TpivPP)-( )]•2( ) has also been determined. Crystal and refinement data: monoclinic; P2,/c; Z = 4; a = 16.951 (3), b = 18.153 (4), c = 25.470 (4) Á; ß = 107.14 (8)°; R = 0.17, Pw = 0.15 for 1521 reflections having / > a¡. The best data obtainable were severely limited in extent (2f)max = 29.2°) and quality, and the resultant structure analysis is therefore only semiquantitative. Dioxygen adopts the end-on bent bond mode of coordination found for Fe(TpivPP)( 1 -Me-imid)(02); the Fe-S separation is 2.49 (2) A, the Fe-N^pj, separations are in the range of 1.99-2.00 A, and the dihedral angle between the least-squares planes of the porphinato skeleton and THT axial base is 44°.

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Diaqua-2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12,3,1]octadeca-1(18),2,12,14,16-pentaeneiron(II) chloride perchlorate

Cited by 21 publications

References 1 publication

DFT Analysis of Spin Crossover in Mn(III) Complexes: Is a Two-Electron S = 2 to S = 0 Spin Transition Feasible?

DFT Analysis of Spin Crossover in Mn(III) Complexes: Is a Two-Electron S = 2 to S = 0 Spin Transition Feasible?

Iron(II) Polyamine Chemistry: Variation of Spin State and Coordination Number in Solid State and Solution with Iron(II) Tris(2-pyridylmethyl)amine Complexes

Pentagonal-bipyramidal complexes. Crystal and molecular structures of chloroaqua(2,6-diacetylpyridine bis(semicarbazone))manganese(II), -iron(II), -cobalt(II), and -zinc(II) chloride dihydrates

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