TY - JOUR
T1 - 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
AU - GalsbØl, Frode
AU - Kojima, Masaaki
AU - Ishii, Toshio
AU - Ohba, Shigeru
AU - Saito, Yoshihiko
AU - Fujita, Junnosuke
PY - 1986/6
Y1 - 1986/6
N2 - 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.
AB - 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.
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U2 - 10.1246/bcsj.59.1701
DO - 10.1246/bcsj.59.1701
M3 - Article
AN - SCOPUS:33748526656
VL - 59
SP - 1701
EP - 1707
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 6
ER -