SYNTHESIS, CHARACTERIZATION AND CHEMISTRY OF SOME LONG-CHAIN ALKOXYCARBONYL MANGANESE PENTACARBONYL COMPLEXES [MN(CO)(5)(C(O)OR)] (WHERE R = N-C7H15 TO N-C10H21, N-C12H25, N-C14H29, AND N-C16H33)

The long chain alkoxycarbonyl complexes, [Mn(CO)(5){C(O)OR}], where R = CH2R', and R = n-C7H15 to n-C10H21, n-C12H25 and n-C16H33, have been synthesized by the reactions of the acyl complexes [Mn(CO)(5){C(O)R'} ], where R' = n-C6H13 to n-C9H19, n-C11H23 and n-C15H31, with synthesi s gas in hexane. In addition, the complexes [Mn(CO)(5){C(O)OR}] (R = n -C9H19 and n-C14H29) have been synthesized by the reactions of the alk yl complexes [Mn(CO)(5)R ''], where R '' = n-C8H17 and n-C13H27, with synthesis gas in hexane. These new alkoxycarbonyl complexes have been fully characterized by elemental analysis, melting point, IR, H-1-NMR, C-13-NMR and mass spectroscopy. The thermal behaviour of these comple xes has been investigated by differential scanning calorimetry and the rmal gravimetry analysis. The reaction of the acyl complex [Mn(CO)(5){ C(O)C11H23}] with synthesis gas in THF gave [Mn-2(CO)(10)] (95%) and t he alcohol n-C12H25OH (92%). The reaction of the alkoxycarbonyl comple x [Mn(CO)(5){C(O)OC12H25}] with synthesis gas in hexane at 85 degrees C gave the formate HCO2C12H25 (66%), the alcohol n-C12H25OH (33%) and [Mn-2(CO)(10)] (96%). The same reaction as above in THF yielded the fo rmate HCO2C12H25 (12%), the alcohol n-C12H25OH (46%) and the ester CH3 (CH2)(3)CO2C12H25 (43%) as well as [Mn-2(CO)(10)] (63%). These studies show that the reactions of the acyl complexes [Mn(CO)(5){C(O)R'}], th e alkyl complexes [Mn(CO)(5)R ''] and the alkoxycarbonyl complexes [Mn (CO)(5){C(O)OR}] with synthesis gas are both solvent and temperature d ependent. (C) 1998 Elsevier Science S.A. All rights reserved.