176302-00-4Relevant academic research and scientific papers
Isothiocyanato complexes of rhenium VI. Synthesis, characterization and structures of cis-and trans-[ReCl2(NCS)(Me2PhP)3]
Huebener, Rainer,Ortner, Kirstin,Straehle, Joachim,Abram, Ulrich
, p. 109 - 114 (1996)
The reaction of [ReCl3(Me2PhP)3] with excess KSCN or trimethylsilylisothiocyanate leads to the replacement of only one chloro ligand. Initially, mer,trans-[ReCl2(NCS) (Me2PhP)3] is formed. The compound crystallizes in the monoclinic space group P21/n with a unit cell of dimensions a = 14.992(2), b = 10.846(1), c = 19.117(6) A, β = 112.89(2)°, Z=4. The chloro ligands are coordinated in trans position to each other. An Re-N bond length of 2.071(4) A was found for the nitrogen bound NCS- ligand. Mer,trans-[ReCl2(NCS)(Me2PhP)3] isomerizes to mer,cis-[ReCl2(NCS) (Me2PhP)3] at longer reaction periods. The cis complex crystallizes in the monoclinic space group P21/n, Z=4. A unit cell of dimensions a = 14.824(7), b = 13.158(2), c = 16.212(7) A, β=112.92(2)° was determined for this compound. The rhenium atom is six-coordinate with cis-positioned chloro ligands. The Re-N bond distance is shortened by 0.038 A with respect to mer,trans-[ReCl2(NCS) (Me2PhP)3]. The coordination geometry of the two isomers of mer-[ReCl2(NCS) (Me2PhP)3] can be derived from FAB-MS studies. Fragmentation occurs by the loss of complete ligands. It takes place in a strong dependence on the structural trans influences of the coordinated ligands. The relative intensities of the main fragments clearly indicate the geometry of the coordination sphere.
