Preparation and characterization of [RhCl2(edpp)2]+ (edpp=(2-aminoethyl)-diphenylphosphine). Crystal Structures of trans(Cl,Cl), cis(P,P)-[RhCl2(edpp)2]Cl·2C2H5OH and cis(Cl,Cl),trans(P,P)-[RhCl2(edpp)2]Cl·4H2O

Frode GalsbØl, Masaaki Kojima, Toshio Ishii, Shigeru Ohba, Yoshihiko Saito, Junnosuke Fujita

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Abstract

Two of the five possible geometrical isomers of [RhCl2(edpp)2]+ were formed by reaction of RhCl3 · 2H20 with edpp (edpp=(2-aminoethyl)diphenylphosphine) in 1:2 molar ratio in ethanol. The chlorides of the isomers were separated by fractional crystallization from ethanol. The structures of the more soluble (main product) and the less soluble (minor product) complexes were determined by X-ray analyses to have the trans(Cl,Cl), cis(P,P) and cis(Cl,Cl), trans(P,P) configurations, respectively. Crystal data are: for trans(Cl,Cl), cis(P,P)-[RhCl2(edpp)2]Cl-2C2H5OH, triclinic, space group P1, with a= 10.024(3), b=18.865(3), c=9.833(2) Å, α=97.66(l), β=103.92(2), γ=82.30(2)°, and Z=2, and for cic(Cl,Cl), trans(P,P)-[RhCl2(edpp)2]Cl·4H2O, triclinic, space group P1, with a= 11.341(4), b=17.780(6), c=8.712(3) Å, α=95.60(4), β=112.31(3), γ=82.56(4)°, and Z=2. The trans influence of the P atom on the Rh-N and Rh-P bond lengths is observed. The mean Rh-N and Rh-P bond lengths (2.125(4) and 2.300(1)Å) in the trans(Cl,Cl), cis(P,P) isomer are respectively longer and shorter than those of the cis(Cl,Cl), trans(P,P) isomer (2.078(12) and 2.336(3)Åt). 13C NMR and absorption spectra of the isomers were recorded and are discussed.

Original languageEnglish
Pages (from-to)1701-1707
Number of pages7
JournalBulletin of the Chemical Society of Japan
Volume59
Issue number6
DOIs
Publication statusPublished - 1986 Jun

ASJC Scopus subject areas

  • Chemistry(all)

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