Magnetism, electronic spectra, and structure of transition metal alkoxides. I. methoxides and ethoxides of chromium(II), manganese(II), Iron(II), cobalt(II), nickel(II), copper(II), titanium(III), chromium(III), and iron(III)

1966 ◽  
Vol 19 (2) ◽  
pp. 207 ◽  
Author(s):  
RW Adams ◽  
E Bishop ◽  
RL Martin ◽  
G Winter

The magnetic moments and electronic spectra are reported for the following divalent transition metal methoxides: Cr(OCH3)2, Mn(OCH3)2, Fe(OCH3)2, Co(OCH3)2, Ni(OCH3)2, and Cu(OCH3)2. These measurements when coupled with the involatility and insolubility of the compounds favour structures based on infinite lattices composed either of regular (Mn, Fe, Co, and Ni) or distorted (Cr and Cu) MO6 octahedra. The spectral data place the ligand field parameter, Δ, for the methoxide group very close to that of water.

1970 ◽  
Vol 23 (1) ◽  
pp. 15 ◽  
Author(s):  
GA Kakos ◽  
G Winter

The compounds VCl(Ome2 (1), VCl(OMe)2,MeCOMe (2), VCl(OMe)2,MeOH (3), and VCl2(OMe),2MeOH (4) were prepared. From magnetic and other physical measurements it is concluded that in (1) the vanadium atoms form trimeric clusters which associate through chlorine bridges to form an infinite lattice. Similar basic units are proposed for (2), but separated from each other by solvent molecules. Two forms of (3) were isolated from the same solution; a soluble trimeric form (A) for which a structure similar to that of (2) is suggested, and an insoluble tetrameric form (B) where the vanadium atoms are situated at the corners of a rhombus. For (4) a structure involving three octahedra, sharing corners (methoxy bridges), is suggested.


1967 ◽  
Vol 20 (11) ◽  
pp. 2343 ◽  
Author(s):  
GA Kakos ◽  
G Winter

The series Co(OMe)X where X = Cl, Br, and I have been prepared and their magnetism and electronic spectra examined. The results clearly show the effect of increasing ligand size on the stereochemistry of the alkoxide. Whereas Co(OMe)I appears to be octahedral and unable to solvate, Co(OMe)Br is tetrahedral but is capable of solvation by methanol to form an octahedral species. Co(OMe)I is tetrahedral and apparently incapable of solvation.


1970 ◽  
Vol 23 (1) ◽  
pp. 1 ◽  
Author(s):  
AG Krueger ◽  
G Winter

The results of magnetic and spectral measurements of Ni(OMe)Cl and its solvates are interpreted in terms of clusters of four nickel atoms interacting ferromagnetically through 90� methoxy bridges. It is proposed that these clusters associate through chlorine bridges to form an infinite lattice. Solvation by methanol breaks only chlorine bridges so that the magnetic clusters are preserved. Stepwise replacement of chlorine by methoxyl resulted in the isolation of the expected compounds of composition Ni3(OMe)4Cl2 and Ni3(OMe)5Cl. Here, the magnetic isolation of the clusters disturbed by antiferromagnetic intercluster exchange. Bromine and iodine bridges also promote antiferromagnetic exchange but in contrast to the methoxy bridges, they may be broken by solvation with methanol.


1967 ◽  
Vol 20 (11) ◽  
pp. 2351 ◽  
Author(s):  
RW Adams ◽  
CG Barraclough ◽  
RL Martin ◽  
G Winter

Najor differences in magnetism are observed in the series CuXL where X = -OMe, Cl, Br, and L = -OMe, acac. Cu(OMe), exhibits linear antiferro- magnetism, CuCl(OMe) follows the Curie law with μeff 2.0 B.M., and CuBr(OMe) is only feebly paramagnetic. The magnetism of Cu(OMe) acac may be interpreted in terms of a singlet-triplet equilibrium with -J = 725 cm-1 (2.08 kcal mole-1).


1956 ◽  
Vol 10 ◽  
pp. 1501-1503 ◽  
Author(s):  
Ole Bostrup ◽  
Chr. Klixbüll Jørgensen ◽  
R. A. Cox ◽  
A. R. Peacocke

1968 ◽  
Vol 21 (6) ◽  
pp. 1461 ◽  
Author(s):  
L Dubicki ◽  
GA Kakos ◽  
G Winter

In the compound Cr(OMe)C12,2CH3OH one molecule of methanol can be replaced by one molecule of acetone, acetonitrile, or dioxan. The magnetism and spectra are interpreted in terms of dimeric models. On heating the dimethanolate one molecule of methanol is lost and for this compound a tetrameric structure is proposed.


1975 ◽  
Vol 30 (11-12) ◽  
pp. 970-972 ◽  
Author(s):  
Claus Friebel

From EPR and ligand field parameter some significant structural details of Cu(II)-compounds can be determined to a notable accuracy: a) the symmetry (tetragonal or orhombic) of Jahn-Teller distorted octahedral Cu(II)-sites, and b) the ordering of Jahn-Teller coupled Cu(II)-polyhedra with respect to each other as well as to the crystallographic axes of the Cu(II)-compound under investigation.


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