Preparation and characterization of cis- And trans- [RhCl 2(dmap)2]+ (dmap=1,3-bis(dimethylarsino)propane), and X-Ray structure analyses of these complexes and irara-[CoCl2(dmap)2]+

Kim Simonsen, Masatoshi Hamada, Nahomi Suzuki, Masaaki Kojima, Shigeru Ohba, Frode Galsbol, Yoshihiko Saito, Junnosuke Fujita

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The cis- and trans- [RhCl2(dmap)2]+ (dmap=1,3-bis(dimethylarsino)propane) complexes were prepared by reaction of RhCl3 · 3H2O with dmap, and the molecular structures of these complexes were determined by the single crystal X-ray diffraction method. Crystal data and final R values are: trans-[RhCl 2(dmap)2]C104 (1), monoclinic, Cc, α=20.018(4), 6=10.229(1), c=12.972(2)̊, β=99.98(2)°, V=2616(1) ̊3 Z=4, R=0.034 for 1298 observed unique reflections. cis-[RhCl2(dmap)2]PF6 (2a), orthorhombic, Pca2 1, α=14.699(2), 6=9.367(2), c=19.640(9) ̊, V=2704(1) ̊,3 Z=4, R=0.086 for 1284 reflections. cis-[RhCl 2(dmap)2]CF3SO3 (2b), orthorhombic, Pca21, α=14.700(3), 6=9.381(4), c=19.644(8) ̊, V=2709(2) ̊, Z=4, R=0.088 for 1094 reflections. The RhAs distances in the linear As-Rh-As groups are 2.442(4)-2.454(4) ̊ (av 2.446(4) ̊) for (1), 2.345(4) and 2.484(6) (av 2.415(6) ̊) for (2a), and 2.389(10) and 2.441(10) ̊ (av 2.415(10) ̊) for (2b), while those in the linear As-Rh-Cl groups are 2.385(3) and 2.370(4) ̊ (av 2.378(4) ̊) for (2a), and 2.387(4) and 2.367(5) ̊ (av 2.377(5) ̊) for (2b). The molecular structure of trans-[CoCl2(dmap)2]ClO4 (3) was also determined by the X-ray method. Crystal data and the final R value are: orthorhombic, Pccm, a=8.018(2), b=8.428(1), c=18.716(3) ̊, V=1265 ̊3, Z=2, R=0.095 for 1072 reflections. A series of trans-[RhX2(dmap)2]+ (X=Cl, Br, I) were prepared and their absorption spectra were compared with one another and with those of related complexes.

Original languageEnglish
Pages (from-to)2904-2910
Number of pages7
JournalBulletin of the Chemical Society of Japan
Issue number10
Publication statusPublished - 1990

ASJC Scopus subject areas

  • Chemistry(all)


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