Crystal structure of Tris(2-methyl-1,10-phenanthroline)iron(II) tetraphenylborate

Goodwin, HA; Kucharski, ES; White, AH

doi:10.1071/ch9831115

Cited by 24 publications

(9 citation statements)

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“…The other type of exceptions stems from the steric hindrance caused by the ligand in the vicinity of the metal center. Complexes [Fe(6-Mebpy) 3 ], [Fe(2-Mephen) 3 ], and [Fe(2-pyq) 3 ] contain a methyl substituent or an additional phenylene ring next to the coordinating N atom, thus introducing a substantial crowding in the coordination sphere of the metal ion. Consequently, the Fe–N distances elongate to relieve the steric repulsion, and the complexes adopt the HS state (with L = 2-Mephen) or demonstrate SCO behavior (with L = 6-Mebpy or 2-pyq).…”

Section: Resultsmentioning

confidence: 99%

A Simple Approach for Predicting the Spin State of Homoleptic Fe(II) Tris-diimine Complexes

et al. 2017

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We propose a simple method for predicting the spin state of homoleptic complexes of the Fe(II) d ion with chelating diimine ligands. The approach is based on the analysis of a single metric parameter within a free (noncoordinated) ligand: the interatomic separation between the N-donor metal-binding sites. An extensive analysis of existing complexes allows the determination of critical N···N distances that dictate the regions of stability for the high-spin and low-spin complexes, as well as the intermediate range in which the magnetic bistability (spin crossover) can be observed. The prediction has been tested on several complexes that demonstrate the validity of our method.

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Section: Resultsmentioning

confidence: 99%

A Simple Approach for Predicting the Spin State of Homoleptic Fe(II) Tris-diimine Complexes

et al. 2017

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“…If the substituent is adjacent to a donor atom this will de-stabilise the singlet state by hindering the close approach of the metal atom and is illustrated by [Fe(mephen) 3 ] 2+ (mephen = 2-methyl-1,10-phenanthroline) which is HS at room temperature but undergoes a transition to LS at low temperatures, in contrast to the unsubstituted [Fe(phen) 3 ] 2+ which is LS at all accessible temperatures. 10 In other instances where the substituent is remote from the donor atom electronic effects may be operative and could be applied to stabilise either state. (ii) The replacement of six-membered heterocycles by fivemembered.…”

Section: Generation Of the Crossover Situationmentioning

confidence: 99%

Spin crossover phenomena in Fe(ii) complexes

2000

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The behaviour of spin crossover compounds is among the most striking and fascinating shown by relatively simple molecular species. This review aims to draw attention to the various ways in which spin crossover phenomena are manifested in iron(II) complexes, to offer some rationalisation for these, and to highlight their possible applications. Typical examples have been selected along with more recent ones in order to give an overall view of the scope and development of the area. The article is structured to provide the basic material for those who wish to enter the field of spin crossover.

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“…This spin crossover is mainly a cooperative phenomenon which passes the information from one molecule or one state of the molecule to the other. , The first ever developed Fe(II) spin crossover system dates back to the 1960s when [Fe(phen) 2 (NCS) 2 ] (phen = 1,10-phenanthroline) was synthesized . Thereafter the research in this field was quite contagious. − …”

Section: Introductionmentioning

confidence: 99%

Lattice-Dictated Conformers in Bis(pyrazolyl)pyridine-Based Iron(II) Complexes: Mössbauer, NMR, and Magnetic Studies

Manikandan

Padmakumar

et al. 2001

Inorg. Chem.

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Iron(II) complexes [FeL(2)](ClO(4))(2).CH(3)CN, [FeL(2)](BPh(4))(2).2CH(3)CN, and [FeL(2)](PF(6))(2) with an FeN(6) chromophore of the same ligand L (2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine) and differing counterions have been made and their crystal and molecular structures determined. The first two crystallized in triclinic space group P(-)1, and the third, with PF(6)(-) anion in Ibca space group. The FeL(2) complex ions in all lattices have similarly distorted octahedral geometry. Variable-temperature Mössbauer spectra of [FeL(2)](ClO(4))(2).CH(3)CN and [FeL(2)](PF(6))(2) measured in the temperature range 1.7-300 K reveal temperature-dependent populations of two different spin states with increased amount of low-spin form at high temperatures, a phenomenon unlike the normal spin crossover behavior; this abnormal behavior is interpreted here as due to the presence of two different conformations. It is very interesting to note that the two different compounds have similar spectra, Mössbauer parameters, and temperature dependence. But the variable-temperature Mössbauer spectra of [FeL(2)](BPh(4))(2).2CH(3)CN in the range 20-300 K do not show the presence of such different species but exhibit a clear phase transition at approximately 200 K. This phase transition is further supported by SQUID measurements. The results of variable-temperature (1)H NMR in CD(3)CN and the solution susceptibility measurement of all complexes also support the presence of high-spin and low-spin forms in solution. Hence, the complex ion [FeL(2)](2+) exhibits a thermally driven interconversion between low-spin and a high-spin structural forms-a phenomenon observed in the solid and solution states due to ligand dynamics. This is not due to the well-known spin crossover phenomenon. These results are compared with the case of normal spin crossover seen in [FeL'(2)](ClO(4))(2) (L' = 2,6-(bis(pyrazol-1-ylmethyl)pyridine)).

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Crystal structure of Tris(2-methyl-1,10-phenanthroline)iron(II) tetraphenylborate

Cited by 24 publications

References 0 publications

A Simple Approach for Predicting the Spin State of Homoleptic Fe(II) Tris-diimine Complexes

A Simple Approach for Predicting the Spin State of Homoleptic Fe(II) Tris-diimine Complexes

Spin crossover phenomena in Fe(ii) complexes

Lattice-Dictated Conformers in Bis(pyrazolyl)pyridine-Based Iron(II) Complexes: Mössbauer, NMR, and Magnetic Studies

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