An electrospray study of rhodium(I) with bidentate phosphines and the preparation and characterization of other ligands

Part I. Electrospray mass spectrometry, ESMS, was used to probe the solution chemistry of rhodium(I) complexes of the type [Rh(COD){lcub}Ph ₂P(CH₂)_nPPh₂{rcub}]_x[BF ₄]_x and [Rh(CO)_y{lcub}Ph₂P(CH₂) _nPPh₂{rcub}]BF₄ (n = 4, 8, 10, or 12; x = 1 or 2; y = 1, 2, or 3). Complementary techniques such as 31P NMR and FAB MS were also used to verify the observations.; Formation of monomer was observed for the short backbone (n = 4) and a mixture of monomer and dimer for those with longer backbones (n = 8, 10, 12). The amount of monomer vs dimer formed was determined by both ESMS and 31P NMR and seems to depend largely on reaction conditions. The cyclooctadiene complexes are cis while the carbonyls are always trans.; By increasing the cone voltage in ESMS, C-H insertion and hydrogen-transfer in these complexes was studied. Loss of hydrogen, formaldehyde, and methanol was observed. Of the three long-chain bis-phosphines (n = 8, 10, and 12) ease of dehydrogenation increased as chain length decreased. Formation of methanol was also favored as chain length decreased. DPPH underwent only a single dehydrogenation.; Study of DPPB indicated a different process involving the bis-phosphine forming and losing HPPh₂ and 1,3-butadiene.; Part II. Dodecyl- and octadecyliminodiacetic acid were also synthesized and complexed with a variety of metals to study their potential usefulness in environmental clean-up. However, both ligands were found to primarily form insoluble ML₂-type complexes or metal hydroxides rendering them ineffective.; Part III. Synthesis of novel mixed arsine-phosphine ligands were attempted by reacting LiAsPh₂ with several different phosphonium salts. The novel complex [Ph₃P(CH₂) ₃AsPh₂]I was formed, along with Ph₂As(CH ₂)₃AsPh₂, from reaction of LiAsPh₂ with [Ph₃P(CH₂)₃I]I.