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Diphosphine and Diarsine Complexes of Chromium(III). Crystal and Molecular Structure of n4>

DOI: 10.1039/DT9830002573

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2573 - 2580 (1983)

Update date:2022-08-03

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Authors:

Gray, Leslie R.Gray, Leslie R.

Hale, Annette L.Hale, Annette L.

Levason, WilliamLevason, William

McCullough, Francis P.McCullough, Francis P.

Webster, MichaelWebster, Michael

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Article abstract of DOI:10.1039/DT9830002573

cis-- ions (X=Cl, Br, or I; L-L=diphosphine or diarsine) have been isolated as tetra-alkylammonium salts by reaction of X, (thf=tetrahydrofuran) , and L-L.The reaction of with L-L' in CH2Cl2 gave Cr(L-L')1.5X3 , which are formulated as trans-cis-.In the case of o-C6H4(PMe2)2 only, it is possible to isolate both Cr1.5X3 and 2X2>X depending upon the Cr:L-L ratio.The ligand Me2As(CH2)3AsMe2 gave Cr(L-L)1.5X3 (X=Cl or Br) complexes for which a ligand-bridged structure is proposed .Weaker donors (Ph2PCH2CH2PPh2, cis-Ph2PCHCHPPh2, or Ph2AsCH2CH2AsPh2) react with to give which contain one uni- and one bi-dentate diphosphine or diarsine, and in the presence of moisture can be isolated.The complexes Y - or PF6-; L-L=o-C6H4(AsMe2)2 or o-C6H4(PMe2)2> have also been obtained.The complexes have been characterised by analysis, conductance, i.r. and electronic spectroscopy, and the electronic spectra analysed (d3) to produce Dq, B', and β35.The title complex is triclinic, a=17.534(3), b=11.930(2), c=11.108(3) Angstroem, α=116.30(2), β=75.12(2), γ=110.61(1) deg, and Z=2; space group P1 (no. 2). 1757 Reflections were refined to R=0.0656 (R'=0.0658).The structure consist of tetrahedral NPrn4+ cations, and pseudo-octahedral - anions.In the anion Cr-P=2.485(4) and 2.511(4) Angstroem; Cr-Cl=2.2331(4), 2.319(4), 2.318(4), and 2.316(4) Angstroem; P-Cr-P=81.2 deg.The diphosphine does not exert any trans influence, consistent with weak binding to the hard CrIII ion.

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