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Aryl Compounds of Rhodium: Syntheses and X-Ray Crystal Structures

DOI: 10.1039/DT9910002821

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2821 - 2830 (1991)

Update date:2022-09-26

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Authors:

Hay-Motherwell, Robyn S.Hay-Motherwell, Robyn S.

Koschmieder, Stefan U.Koschmieder, Stefan U.

Wilkinson, GeoffreyWilkinson, Geoffrey

Hussain-Bates, BilquisHussain-Bates, Bilquis

Hursthouse, Michael B.Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9910002821

The interactions of fac-RhCl3(tht)3, tht = tetrahydrothiophene, with aryl-lithium or -magnesium bromide reagents, aryl = 2,4,6-R3C6H2 ( R = Me or Pri), 2,6-Me2C6H3, or 2-MeC6H4, and also Mg(PhCH2)Br, have been studied.With Li(2,4,6-Pri3C6H2)(Et2O) only the unique, square, paramagnetic rhodium(II) compound trans-Rh(2,4,6-Pri3C6H2)2(tht)2 is obtained.This reacts with CO reversibly to give labile carbonyl species and with ButNC to give the rhodium(I) ?-bonded iminoacyl Rh(CNBut)3(2,4,6-Pri3C6H2C=NBut).A similar mesityl (mes) compound is obtained from Rh(mes)3 and ButNC.Homoleptic rhodium(III) aryls Rh(aryl)3 have been obtained for aryl = 2,6-Me2C6H3 and 2,4,6-Me3C6H2.The mesityl reacts with CO to give a carbonyl species that has a bridged acyl and a bridge in which a mesityl group ?-bonded to one Rh atom is bound η6 to the other.It also reacts with PMe2Ph to give Rh(mes)(PMe2Ph)3.The interaction of RhCl3(tht)3 with Mg(PhCH2)Br gives only the unsymmetric bridged species (tht)(PhCH2)2Rh(μ-Cl)3Rh(CH2Ph)(tht)2.The crystal structures of six compounds have been determined: trans-Rh(2,4,6-Pri3C6H2)2(tht)2 is square with a two-fold axis of symmetry perpendicular to the molecular plane .The compounds Rh(CNBut)3(?-RC=NBut), (R = 2,4,6-Me3C6H2 or 2,4,6-Pri3C6H2) have similar structures in which the rhodium(I) centres are square .The compound Rh2(2,4,6-Me3C6H2CO)(2,4,6-Me3C6H2(CO)3 contains two rhodium centres with quite different co-ordination: Rh(1) is square with bonds to two carbonyls , an aryl and an oxygen from the aroyl ligand ; Rh(2) is trigonal bipyramidal with the aryl ?-bonded to Rh(1) now η6 bonded over two equatorial and one axial sites, the remaining axial and equatorial sites being occupied by the aroyl carbon and a carbonyl group .The compound Rh(2,4,6-Me3C6H2)(PMe2Ph)3 has square rhodium(I) geometry .The dimer Rh2(PhCH2)3Cl3(tht)3 has a confacial bioctahedral structure with Rh-Cl, Rh-C and Rh-S distances showing considerable variations due to the differing trans influences of the three ligand types.

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