NDLI: Selective formation of cis-diacyl , $cis-PPh_{2}R$ rhodium(III) complexes by the reaction of rhodium (III) cis-diacyl , trans-PPh $

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Hernández, Ricardo Zarandona, Malkoa Torres, M. Rosario Garralda, María A. Pinilla, Elena
Description	Author Affiliation: Garralda MA ( Facultad de Química de San Sebastián, Universidad del País Vasco, Apdo. 1072, 20080, San Sebastián, Spain. mariaangeles.garralda@ehu.es)
Abstract	The cis-diacyl , trans-PPh $_{2}R$ complex $[RhCl(PPh_{2}(o-C_{6}H_{4}CO))_{2}(pyridine)]$ (1) reacts with substituted aliphatic diamines to afford selectively cationic cis-diacyl , cis-PPh $_{2}R$ , diamine derivatives $[Rh(PPh_{2}(o-C_{6}H_{4}CO))_{2}(NN′)]^{+}$ ( NN′ = 1,2-diphenylethylenediamine , 2; 1,2-propanediamine , 3; N-methylethylenediamine , 4; N,N-dimethylethylenediamine , 5; N,N′-dimethylethylenediamine , 6; N,N,N′-trimethylethylenediamine , 7) with high stereoselectivity depending on the N -donor ligand employed. Complexes 2 and 3 contain a single isomer, while 4 is a mixture of two isomers, 4a and 4b. Formation of 4a occurs first and is followed by isomerisation to 4b until the equilibrium 4a:4b = 1:4 ratio is attained. In contrast, 5 and 6 contain a single isomer. More basic amino groups prefer positions trans to an acyl group while less basic amino groups are trans to a phosphine group . The preferred intramolecular N—H⋯O hydrogen bond formation between an amino and an acyl coordinated ligands, trans to the phosphorus atoms, appears to be relevant to the selectivity observed. 7 is a mixture of two isomers 7a and 7b in a 7a:7b = 5.7:1 ratio. N,N,N′,N′-tetramethylethylenediamine or N,N′-diphenylethylenediamine led to the elimination of the N -donor ligands and the formation of a mixture of isomers of $[Rh_{2}(μ-Cl)(μ-PPh_{2}(o-C_{6}H_{4}CO))_{2}(PPh_{2}(o-C_{6}H_{4}CO))_{2}]^{+}$ (8), where the Rh atoms are triply bridged by two acyl groups in a head-to-tail arrangement and by a chloride . The reaction of $[Rh(PPh_{2}(o-C_{6}H_{4}CO))_{2}(ndmeen)]ClO_{4}$ (5) with acids led to the displacement of the diamine and the formation of a $[8a]^{+}:[8b]^{+}:[8c]^{+}$ = 1:1:3 mixture. 8c, containing the weakest σ-donor oxygen atoms trans to the strongest σ-donor acyl groups , represents the most electronically favourable geometry for 8. All the complexes were fully characterized spectroscopically. Single crystal X-ray diffraction analysis was performed on 5, 6, 8a and 8b.
ISSN	14779226
Journal	Dalton Trans.
Issue Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2009-11-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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