35429-67-5Relevant academic research and scientific papers
Synthesis, characterization, and reactivity of alkoxide and hydroxide complexes of rhodium(I) and iridium(I)
Green, Lisa M.,Meek, Devon W.
, p. 659 - 666 (2008/10/08)
Bimetallic alkoxide- and hydroxide-bridged complexes of rhodium(I) and iridium(I), [M(OR)COD]2 (M = Rh, Ir; R = H, alkyl or aryl group; COD = 1,5-cyclooctadiene), were prepared and used in the synthesis of four-coordinate alkoxide and hydroxide complexes of rhodium(I) and iridium(I) containing the chelating triphosphine ligands ttp {C6H5P[CH2CH2CH2P(C 6H5)2]2} or Cyttp {C6H5P[CH2CH2CH2P(C 6H11)2]2}, i.e. M(OR)(ttp) or M(OR)(Cyttp). The basicity of the Rh-OR bond in Rh(OH)(ttp) and Rh(OC6H5)(ttp) was tested by use of reactions with weak organic acids; consequently, a series of rhodium carboxylates (e.g., Rh(OC(O)CF3)(ttp), Rh(OC(O)C6H4Br)(ttp), and Rh(OC(O)C6H5)(ttp)) was formed. Sulfur dioxide insertion reactions led to metal sulfonates and metal sulfonic acids, i.e. Rh(SO2OC6H6)(ttp)·SO2, Rh-(SO2OC6H5)(Cyttp)-SO2, Ir(SO2OC6H6)(ttp)·SO2, and Rh(SO2OH)(ttp)·SO2. The three olefins (CH2=CH2, Cl2C=CClH, and (CN)2O=C(CN)2) failed to react with Rh(OH)(ttp) or Rh(OC6H5)(ttp) to produce insertion products or simple olefin adducts. All metal complexes were characterized by elemental analysis and infrared and 31P{1H} NMR spectroscopy.
