Reaction of CpRu(PPh3)(2)Cl with six-member cyclothioethers. Structures of the [CpRu(PPh3)(x)L]Y complexes (L = pentamethylene sulfide, x=2, Y=BF4-; L = 1,3-dithiane; 1,3,5-trithiane, x=2, Y=CF3SO3-; L=1,4-dithiane, x=1, Y=BF4-)
by Green, M.; Draganjac, M.; Jiang, Y. J.; Nave, P. M.; Cordes, A. W.; Bryan, C. D.; Dixon, J. K.; Folkert, S. L.; Yu, C. H.
The synthesis of a series of ruthenium complexes with cyclothioether ligands is reported. The compounds were characterized by X-ray diffraction techniques. The molecular structures of [CpRu(PPh3)(2)(pms)] BF4 (1), [CpRu(PPh3)(2)(1,3-dithiane)] OTfl (2), [CpRu(PPh3)(2)(1,3,5-trithiane)] OTfl (3), and [CpRu(PPh3)(1,4-dithiane)] BF4 ( 4) show chelation occurs only when the sulfur atoms are separated by at least two C atoms, creating a ligand bite size large enough to chelate. Cell parameters: 1, space group P2(1)/c, a = 14.601(4), b = 19.102(10), c = 14.751(7) Angstrom, beta = 98.28(3) degrees; 2, space group P2(1)/c, a = 12.859(7), b = 15.576(3), c = 22.126(11) Angstrom, beta = 102.22(4) degrees; 3, space group P2(1)/c, a = 12.7320(20), b = 15.571(5), c = 22.287(4) Angstrom, beta = 101.812(14) degrees; 4, space group Pbca, a = 11.2010(10), b = 16.321(7), c = 28.966( 4) Angstrom. Compounds 2 and 3 are X-ray isomorphous. The Ru-S bond lengths range from 2.341( 3), 2.365( 3)Angstrom in compound 4 to 2.382(4) Angstrom in compound 2. Upon chelation ( compound 4), with subsequent loss of PPh3, the Ru-P bond shortens to 2.327(3) Angstrom. This may be due to reduced steric hindrance about the Ru atom. No evidence for C-S bond lengthening is observed.
- Journal
- Journal of Chemical Crystallography
- Volume
- 33
- Issue
- 5-6
- Year
- 2003
- Start Page
- 473-479
- URL
- https://dx.doi.org/10.1023/a:1024250702433
- ISBN/ISSN
- 1572-8854; 1074-1542
- DOI
- 10.1023/a:1024250702433