Control of Iron(II) Spin States in 2,2′:6′,2″-Terpyridine Complexes through Ligand Substitution

Constable, Edwin C.; Baum, Gerhard; Bill, Eckhard; Dyson, Raylene; Eldik, Rudi van; Fenske, Dieter; Kaderli, Susan; Morris, Darrell; Neubrand, Anton; Neuburger, Markus; Smith, Diane R.; Wieghardt, Karl; Zehnder, Margareta; Zuberbühler, Andreas D.

doi:10.1002/(sici)1521-3765(19990201)5:2<498::aid-chem498>3.0.co;2-v

Cited by 132 publications

(24 citation statements)

References 15 publications

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“…Unsubstituted [Fe(1-bpp) 2 ] 2+ (Scheme 2) is SCO-active, with T ½ = 248 K in (CD 3 ) 2 CO [38], but [Fe(R 2 -1-bpp) 2 ] 2+ are fully high-spin in the same solvent when R = Ph or iPr [39]. The same trend is shown by the isomeric 3-bpp complex series, in that [Fe(3-bpp) 2 ] 2+ itself (Scheme 2) is SCO-active [5] [41].…”

Section: Steric Influence Of Ligand Substituents On Metal Ion Spin Stsupporting

confidence: 86%

“…The same trend is shown by the isomeric 3-bpp complex series, in that [Fe(3-bpp)2] 2+ itself (Scheme 2) is SCO-active [5] but four [Fe(R2-3-bpp)2] 2+ derivatives with R ≠ H are all fully high-spin [40]. Like most derivatives of [Fe(terpy)2] 2+ , [Fe(terpy)2] 2+ itself is low-spin when R = H, but [Fe(Ph2terpy)2] 2+ undergoes SCO (T½ ≈ 300 K in EtCN solution) [41].…”

Section: Steric Influence Of Ligand Substituents On Metal Ion Spin Stmentioning

confidence: 64%

“…In each case, trends observed from solid state data on these compounds mirror the solution phase results [29][30][31][32]36,[38][39][40][41][44][45][46][47] [51,52] and other complexes in Scheme 4 [53,54] with sterically significant distal ligand substituents also exhibit stabilized high-spin states in solid phases. Interestingly, however, [Fe(Mes 2 -1-bpp) 2 ] 2+ presents an exception to the above discussion, being fully low-spin at room temperature despite the steric bulk of its distal mesityl substituents [39,51].…”

Section: Steric Influence Of Ligand Substituents On Metal Ion Spin Stmentioning

confidence: 99%

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The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

2016

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Abstract:The relationship between chemical structure and spin state in a transition metal complex has an important bearing on mechanistic bioinorganic chemistry, catalysis by base metals, and the design of spin crossover materials. The latter provide an ideal testbed for this question, since small changes in spin state energetics can be easily detected from shifts in the spin crossover equilibrium temperature. Published structure-function relationships relating ligand design and spin state from the spin crossover literature give varied results. A sterically crowded ligand sphere favors the expanded metal-ligand bonds associated with the high-spin state. However, steric clashes at the molecular periphery can stabilize either the high-spin or the low-spin state in a predictable way, depending on their effect on ligand conformation. In the absence of steric influences, the picture is less clear since electron-withdrawing ligand substituents are reported to favor the low-spin or the high-spin state in different series of compounds. A recent study has shed light on this conundrum, showing that the electronic influence of a substituent on a coordinated metal ion depends on its position on the ligand framework. Finally, hydrogen bonding to complexes containing peripheral N-H groups consistently stabilizes the low-spin state, where this has been quantified.

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Section: Steric Influence Of Ligand Substituents On Metal Ion Spin Stsupporting

confidence: 86%

Section: Steric Influence Of Ligand Substituents On Metal Ion Spin Stmentioning

confidence: 64%

Section: Steric Influence Of Ligand Substituents On Metal Ion Spin Stmentioning

confidence: 99%

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The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

2016

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“…10 nicely demonstrate this point [15]. The large volume increase observed for the binding and release of NO in the case of substrate-free P450 is partly due to the dissociative character of the process and partly due to a change in spin-state from lowspin to high-spin, which is typically accompanied by a volume increase between 12 and 15 cm 3 mol −1 [16]. In the presence of substrate, the binding of NO is accompanied by a decrease in volume typical for a bond-formation process, followed by a further volume decrease associated with a high-spin to low-spin changeover.…”

Section: Cytochrome P450 and Model Complexessupporting

confidence: 72%

Fascinating inorganic/bioinorganic reaction mechanisms

Eldik

2007

Coordination Chemistry Reviews

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“…[1][2][3][10][11][12][13][14] One of the interesting properties in SCO complexes is that the spin state can be controlled by replacing counter anions and by the subtle modification of ligands. It has been reported that the Fe(II) complex with 2,2′:6′,2′′-terpyridine (tpy) ligand and its derivatives is able to assume an HS or LS state depending on the structure of the coordinated ligands [15] . …”

Section: Introductionmentioning

confidence: 99%

Crystal Structure and Magnetic Properties of a novel Fe(II) complex with 2,2′:6′2′′-Terpyridine Ligand

Zhang

Yao

et al. 2014

Trans. Mat. Res. Soc. Japan

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Control of Iron(II) Spin States in 2,2′:6′,2″-Terpyridine Complexes through Ligand Substitution

Cited by 132 publications

References 15 publications

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

Fascinating inorganic/bioinorganic reaction mechanisms

Crystal Structure and Magnetic Properties of a novel Fe(II) complex with 2,2′:6′2′′-Terpyridine Ligand

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