REACTIVITY OF THE BINUCLEAR HYDRIDE [FE2(CO)4(MU-H)(MU-CO)-(MU-PPH2)(MU-PH2PCH2PPH2)] TO GENERATE PHOSPHIDO AND HYDROXIDE MOIETIES AT THE DIIRON CENTER.
J CHEM SOC DALTON
143 - 150.
Thermolysis of [Fe2(CO)4(mu-H)(mu-CO)(mu-PPh2)(mu-dppm)] 1 (dppm = Ph2PCH2PPh2) results in benzene loss via phosphorus-carbon bond cleavage yielding [Fe2(CO)5(mu-PPh2)(mu-PhPCH2PPh2)] 2. ln a number of other reactions of 1, carbon monoxide and the hydride are replaced by three-electron donor ligands. Chromatography on alumina afforded the bridging hydroxide complex [Fe2(CO)4(mu-OH)(mu-PPh2)(mu-dppm)] 3, while thermolysis in the presence of secondary phosphines gave the bis(phosphido) complexes [Fe2(CO)4(mu-PPh2)(mu-PR2)(mu-dppm)] (R = Ph 4 or C6H11 5). Complexes 2-4 have been characterised crystallographically. All show a diiron centre bridged by two cis three-electron donor ligands. Both 4 and 5 are fluxional on the NMR time-scale, the observed changes being ascribed to a 'rocking' of the phosphido-bridges and a 'twisting' of the diphosphine respectively.
|Title:||REACTIVITY OF THE BINUCLEAR HYDRIDE [FE2(CO)4(MU-H)(MU-CO)-(MU-PPH2)(MU-PH2PCH2PPH2)] TO GENERATE PHOSPHIDO AND HYDROXIDE MOIETIES AT THE DIIRON CENTER|
|Keywords:||MOLECULAR-STRUCTURE, BIS(DIPHENYLPHOSPHINO)METHANE, COMPLEXES, CRYSTAL, HEXACARBONYL, ACTIVATION, GEOMETRY, BOND|
|UCL classification:||UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry|
Archive Staff Only