14593-70-5Relevant academic research and scientific papers
Low temperature matrix photochemistry of M2(CO) 4(μ-S-t-Bu)2 and [M(CO)2Cl2] 1- anions, where M = Rh and Ir
Bitterwolf, Thomas E.,Wong, Byron
, p. 4273 - 4278 (2004)
Photolysis of M2(CO)4(μ-S-t-Bu)2, where M = Rh or Ir, results in loss of CO. Similarly, photolysis of [M(CO) 2Cl2]1- results in CO loss, while Ir(CO)(PMe3)2Cl undergoes a structural change akin to that of its rhodium analogue. Photolysis of M2(CO)4(μ-S-t- Bu)2, where M = Rh or Ir, in Nujol matrices at ca. 90 K results in simple CO loss to form a tricarbonyl intermediate analogous to that observed for Rh2(CO)4(μ-Cl)2. Photolysis of the anions, [M(CO)2Cl2]1-, where M = Rh or Ir, in inert ionic matrices at ca. 90 K, results in CO-loss to form an intermediate analogous to that formed by Rh(CO)2(i-Pr2HN)Cl. Finally, photolysis of trans-Ir(CO)(PMe3)2Cl in a Nujol matrix at ca. 90 K gives rise to a new species whose carbonyl band is shifted slightly down in energy as has been observed for trans-Rh(CO)(PMe3)2Cl. In all cases the iridium compounds behave similarly to the rhodium species although the photon energy for iridium photochemistry is typically above that of the rhodium compounds.
The synthesis, properties, and crystal structure of n-Bu4N, and the exchange of acetate, chloride, and iodide in n-Bu4N
Fulford, Anthony,Bailey, Neil A.,Adams, Harry,Maitlis, Peter M.
, p. 139 - 147 (2007/10/02)
Reaction of nBu4N, 1, with silver acetate under CO gave the diacetate salt nBu4N, 2.The complex has been characterised spectroscopically term) 1986, 2066; ν(CO2-monodentate) 1615 cm-1> and by a single-crystal X-ray determination.The anion is planar with monodentate acetates, Rh-O 2.074(6) and 2.053(7) Angstroem.Comlex 2 reacted immediately with Mel to give MeOAc and -, 3, which then oxidatively added more Mel normally.It also reacted with HCl to give HOAc and -.Evidence was obtained for the formation of a labile mixed anion - on reaction of with nBu4N+OAc-.It is unlikely that the promotional effect of acetate in methyl acetate carbonylation is due to the participation of acetato-rhodium complexes.Since the lithium acetate reacts readily with iodomethane to give lithium iodide, the observed promotion probably arises from the formation of LiI.MeI reacted with nBu4N, again via preliminary formation of nBu4N, which then added MeI normally.IR spectra showed that the equilibrium, 1 +2I- 3 + 2Cl-, favoured the chloride 1 in CH2Cl2, and the iodide 3 in methanol.
