The structure of dichlorobis(phenylamine)(bicyclo[2.2.1]hepta-2,5-diene)ruthenium: A π-bonded norbornadiene complex of ruthenium(II)

• Published in: Journal of organometallic chemistry Vol. 72; no. 2; pp. 247 - 259
• Main Authors: Manoli, Jean-marie, Gaughan, Arthur P., Ibers, James A.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.01.1974
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(00)81498-9

The structure of dichlorobis(aniline)(norbornadiene)ruthenium (aniline = phenylamine, norbornadiene = bicyclo[2.2.1]hepta-2,5-diene), RuCl 2 (C 7H 8)(C 6H 5NH 2) 2, has been determined from three-dimensional X-ray data collected by counter techniques and refined by a least-squares procedure to a conventional agreement index of 0.025. The complex crystallizes in space group C 12 2 v  Cmc2 1 of the orthorhombic system in a cell of dimensions a 17.162(4), b 12.589(3), c 8.522(2) Å, V 1841.3 Å 3 with Z 4. Observed and calculated densities are 1.61(1) and 1.62 g/cm 3. The coordination geometry about the ruthenium atom is distorted octahedral with the norbornadiene moiety bound through the two double bonds. The complex possesses crystallographically imposed C 3(m) symmetry with the trans-chloro ligands, the ruthenium atom, and the three sp 3 carbon atoms of the diolefin constrained to the mirror plane. The coordination sphere is completed by cis-aniline groups. Bond distances of interest are: RuCt (where Ct is the center of the olefinic bond), 2.066(4); RuN, 2.213(3); RuCl, 2.415(2) and 2.407(1) Å. The CC distance of the olefinic bond is 1.386(6) Å, compared with 1.35 Å in the free ligand. The remaining distances in the bicyclic ligand are very close to the expected value for CC single bonds, 1.54 Å. The CtRuCt angle is 70.0° and the ClRuCl angle is 156.5(5)°.