Intermediate spin

Intermediate spinning at half the maximum speed of spinning, i.e. at 8 or 12 pole. 

Kimer JF, Dow W, Scheldt WR. 1976. Molecular stereochemistry of two intermediate-spin complexes. Iron(II) phthalocyanine and manganese(II) phthalocyanine. Inorg Chem 15 1685-1690. 

The method mentioned has been appUed to ClFe(Et2dfc)2 first, because for this compound, and some related ones, an abnormally large QS has been observed, while the crystal field theory predicts QS = 0 for this intermediate spin (S = 3/2) compound. 

A typical example of a correlation diagram for Fe is given in Fig. 4.3. It summarizes the isomer shifts for a great variety of iron complexes with oxidation states (1) to (VI) in the order of the respective high-spin, intermediate-spin, and low-spin configurations. The plot of the corresponding values marked by grey, hatched and open bars demonstrates three major trends ... 

Low-spin compounds exhibit lower isomer shifts than high-spin compounds, whereas the isomer shifts of intermediate-spin compounds often resemble those of the corresponding low-spin compounds. 

Another typical example for anisotropic covalency is found in five-coordinate ferric compounds with intermediate spin S = 3/2 (also discussed in Sect. 8.2). Crystal field theory predicts a vanishing valence contribution to the EFG, whereas large quadrupole splittings up to more than 4 mm s are experimentally found. 

Intermediate spin occurs mainly for square- and rhombic-pyramidal five-coordinate iron complexes and also for planar four-coordinate and for asymmetric six-coordinate... 

Coordination compounds of dianionic dithiolene (S2C2 R2) and benzene-1,2-dithiolene (bdt = (S2C6H4) and their derivatives have been studied since the 1960s by Mossbauer spectroscopy [87] and other techniques. Nevertheless, many aspects of their electronic structure remained uncertain for a long time. The five-coordinate ferric complexes with two equatorial dithiolene ligands exhibit intermediate spin and show the Mossbauer parameters = 0.25-0.38 mm s and A q = 1.6-3.2 mm s For example, [Fe° mnt)2/ y] with two mnt ligands (=S2C2(CN)2) and an... 

The intermediate-spin ground state of the ferric compounds published by Jager and coworkers is also stabilized by a N4-macrocyclic ligand, [N4] which exist in different varieties of substitutions. The apical ligands are weakly coordinating halides or pseudohalides, such as iodide in the case of [Fe [N4]l] (20) [68]. The electronic structure was elucidated by EPR, Mbssbauer and DFT studies. 

In a crystal-field picture, the electronic structure of iron in the five-coordinate compounds is usually best represented by a (d yf idyz, 4cz) ( zO configuration [66, 70], as convincingly borne out by spin-unrestricted DFT calculations on the Jager compound 20 [68]. The intermediate spin configuration with an empty d 2 yi orbital in the CF model, however, has a vanishing valence contribution to the... 

Table 8.3 Mossbauer parameters of iron(II) complexes with intermediate spin (S = 1)...

The true electronic structure might be Fe(III) with intermediate spin (5pe = 3/2), antiferromag-... 

Four-coordinate, planar iron(II)-dithiolate complexes also exhibit intermediate spin. The first example described was the tetraphenylarsonium salt of the square-planar bis(benzene-l,2-dithiolate)iron(II) dianion, (AsPh4)2[Fe(II)bdt2], which showed 5 = 0.44 mm s and AEq = 1.16 mm s at 4.2 K [157]. The electronic structure of a different salt was explored in depth by DFT calculations, magnetic susceptibility, MCD measurements, far-infra red spectroscopy and applied-field Mossbauer spectroscopy [158]. 

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