Add time:09/25/2019         Source:sciencedirect.com

The ligand 1,6-bis(diphenylphosphino)hexane undergoes a dehydrogenation reaction with M2X2(C8H12)2, C8H12 = 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 M2Cl2(C8H12)2 to give the dimeric complexes [M(CO)Cl(ligand)]2 which do not dehydrogenate. The ligands (C6H5)2P(CH2)nP(C6H5)2, n = 5, 7 or 8 and (C6H5)2As(CH2)6As(C6H5)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, 1H N.M.R. spectral and 13C N.M.R. spectral data are consistent with the above reactions and formulations.

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