Arylimido Complexes of Chromium-(VI), -(V) and -(IV)

DOI: 10.1039/DT9950002111

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2111 - 2124 (1995)

Update date:2022-09-26

Topics:

Authors:

Danopoulos, Andreas A.

Wilkinson, Geoffrey

Sweet, Tracy K. N.

Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9950002111

The first arylimido compounds of chromium(VI), CrCl2(NR)2 (R = 2,4,6-Me3H2C6 or 2,6-Me2H3C6), have been made by interaction of CrCl2(N(t-Bu))2 with the aryl isocyanates.Silimar interaction with 2,6-(i-Pr)2C6H3NCO gave a dimeric chromium(V) compound 2.The chloride CrCl2(NC6H2Me3-2,4,6)2 formed adducts with Lewis bases, e.g.CrCl2(NC6H2Me3-2,4,6)2(PMe3)2 and 2 (terpy = 2,2':6',2 -terpyridine) was obtained with AgBF4.Substitution of Cl atoms occurred with NaR' (R'= OSiMe3, OC6H2Me3-2,4,6, SC6H2Me3-2,4,6, SC6F5 or SC6H2(i-Pr)3-2,4,6) and with Grignard reagents, MgR Br (R = CH2CMe3, CH2CMe2Ph or CH2Ph) giving in all cases compounds of the type Cr(NC6H2Me3-2,4,6)2R'2 or Cr(NC6H2Me3-2,4,6)2R 2.The alkyl compounds underwent insertion with (t-Bu)NC, or 2,6-Me2H3C6NC to give η²-iminoacyl compounds of Cr(VI) and reduction by PMe3 on heating to give the chromium(IV) dimer 2.The interaction of CrCl2(NC6H2Me3-2,4,6)2 with the Grignard reagent derived from 4-tert-butylbenzyl chloride gave not a diakyl but an amidochromium(IV) dimer >2, while on interaction with MgEtBr in the presence of PMe3 it gave the dichromium(V) compound (2,4,6-Me3H2C6N)BrCr(μ-NC6H2Me3-2,4,6)2CrBr(NC6H2Me3-2,4,6)(PMe3).The crystal structures of seven compounds have been determined, in six of which the Cr atoms have slightly distorted tetrahedral geometry, while in the remaining compound one atom is tetrahedral and the other five-co-ordinate.The geometries of the Cr2N2 rings in four of the compounds are indicative of some direct Cr...Cr interaction.

Full text of DOI:10.1039/DT9950002111

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