o-Phenylenediamine and Related Complexes of Chromium, Vanadium and Manganese

DOI: 10.1039/DT9920001803

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1803 - 1812 (1992)

Update date:2022-08-05

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Authors:

Redshaw, Carl

Wilkinson, Geoffrey

Hussain-Bates, Bilquis

Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9920001803

Using the ligands (L-L) o-phenylenediamine, 4,5-dimethyl-o-phenylenediamine and phenanthrene-9,10-diamine, anionic chromium(III) complexes of the type ^-, have been isolated as quaternary phosphonium salts from interaction of CrCl3(thf)3 (thf = tetrahydrofuran) and the ligand in the presence of Cl or Cl.Interaction in the presence of quaternary phosphonium salts gives Cl.A similar tetrachloro anion has been obtained using the chelating phosphine 1,2-(HPr¹P)2C6H4.Similar complexes obtained from VCl3(thf)3 have the form ^- and Cl.Use of the dihalides leads to octahedral complexes trans-MCl2(L-L)2 (M = V or Cr) and trans-MnI2(L-L)2.The interaction of > with AgO3SCF3 and of 2>Cl with trifluoromethanesulfonic acid and diethyl ether leads to the unusual chromium(IV) octahedral triflate compounds Cr(NH2)(O3SCF3)3<(H2N)2C6H2Me2> and Cr(O3SCF3)4<(H2N)2C6H4>, respectively.The crystal structures of the compounds >, Cr(NH2(O3SCF3)3<(H2N)2C6H2Me2>, Cr(O3SCF3)4<(H2N)2C6H4> and > have been determined.All have octahedral structures with chelating diamines.In the tetrachlorochromate(III) salt, the Cr-N distances are ca. 0.05 Angstroem longer than those in the chromium(IV) compounds.The V^III-N distances <2.16(1) Angstroem> are ca. 0.05 Angstroem longer than the Cr^III-N distances <2.11(1) Angstroem>, as expected, but the vanadium complex shows a much greater difference in M-Cl distances trans to N <2.336(4) Angstroem> or trans to Cl <2.381(4) Angstroem> than in the chromium(III) complex .

Full text of DOI:10.1039/DT9920001803

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