673457-76-6Relevant academic research and scientific papers
Ligand ambivalence in pallada(platina)cyclic complexes of a rigid phosphine
Malik, K.M. Abdul,Newman, Paul D.
, p. 3516 - 3525 (2007/10/03)
Palladium(II) and platinum(II) complexes of a chiral pentacyclic phosphine, (1S, 4R, 4aS, 5aR, 6R, 9S, 9aS, 10aR)-4,6,11,11,12,12-hexamethyl-10-phenyl-dodecahydro-1,4:6, 9-dimethano-phenoxaphosphinine (phenop), show diverse structures dependent upon the chosen metal-containing starting material and reaction conditions. With palladium acetate, a P,C-cyclometallated dimeric complex [Pd(μ-κ 2-OAc)(μ-κ1-OAc)(κP,κC 14-phenop)]2, 4, is obtained through metallation at the C(14) methyl to form a six-membered chelate. The acetato bridged dimer is readily converted to the halo-bridged species [Pd(μ-X)(κP,κC 14-phenop)]2, where X is chloride (5) or bromide (6). Reaction of one equivalent of phenop with Pd(COD)Cl2 or Na 2PdCl4 gives a different phosphapalladacycle dimer [Pd(μ-Cl)(κP,κC8-phenop)]2, 7, with a five-membered chelate and metallation at the C(8) methylene carbon. The analogous platinum derivative [Pt(μ-Cl)(κP,κC 8-phenop)]2, 8, is obtained from the 1 : 1 reaction of phenop and K2PtCl4. An unusual ligand-ligand coupled product, 9, has been isolated in low yield from the reaction of phenop and Pd(COD)Cl2. The zerovalent Pd(κP-phenop)2, 10, and a monodentate silver(I) derivative, [Ag(κP-phenop)(CF3SO 3)], 11, have also been prepared. These new complexes have been fully characterised by spectroscopic and other techniques including single crystal X-ray structure determinations of phenop, 7-9 and 11.
