P. W. Clark
Sep 13, 1977
Citations
0
Influential Citations
20
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract The ligand 1,6-bis(diphenylphosphino)hexane undergoes a dehydrogenation reaction with M 2 X 2 (C 8 H 12 ) 2 , C 8 H 12 = cis cis cycloocta-1,5-diene to form MX(BDPH), M Rh and X Cl or Br, or M Ir and X C1, and BDPH 1,6-bis(diphenylphosphino)- trans -hex-3-ene. In the presence of carbon monoxide 1,6-bis(diphenylphosphino)hexane and 1,6-bis(diphenylarsino)hexane react with M 2 Cl 2 (C 8 H 12 ) 2 to give the dimeric complexes [M(CO)Cl(ligand)] 2 which do not dehydrogenate. The ligands (C 6 H 5 ) 2 P(CH 2 ) n P(C 6 H 5 ) 2 , n = 5, 7 or 8 and (C 6 H 5 ) 2 As(CH 2 ) 6 As(C 6 H 5 ) 2 do not undergo the dehydrogenation reaction under the same conditions. The ligands 1,6-bis(diphenyl-phosphino)- trans -hex-3-ene and 1,6-bis(diphenylarsino)- trans -hex-3-ene have been prepared and undergo normal substitution reactions with rhodium(I) and iridium(I) complexes. The square-planar complexes MCl(BDPH) react reversibly with carbon monoxide forming fluxional five coordinate complexes M(CO)Cl(BDPH), M Rh or Ir and with excess carbon monoxide to form [M(CO) 2 (BDPH)] + , M Ir, isolated as the tetraphenylborate salt. A possible mechanism for the dehydrogenation reaction is discussed. Analytical, mass spectral, infrared spectral, 1 H N.M.R. spectral and 13 C N.M.R. spectral data are consistent with the above reactions and formulations.