Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.

Issue 4, 1984
Previous Article Next Article

Carbon monoxide reduction. [Fe(η5-C5H5)(Ph2PCH2CH2PPh2)(CO)H]: reactions and formation by reduction of the complex [Fe(η5-C5H5)(Ph2PCH2CH2PPh2)(CO)]PF6


The preparation of the cations of [Fe(η5-C5H5)(dppe)(CO)]PF6(1)(dppe = Ph2PCH2CH2PPh2) and [Fe(η5-C5H5)(PPh3)2(CO)]PF6(5) and their reduction with LiAlH4 to form the complexes [Fe(η5-C5H5)(dppe)(CO)H](2) and [Fe(η5-C5H5)(PPh3)(CO)H](6), respectively, is described. Evidence is presented for the intermediacy of [Fe(η5-C5H5)(dppe)(CHO)](4) in the low-temperature reduction of (1). High-temperature reduction of (1) occurs with loss of regioselectivity yielding both [Fe(η5-C5H5)(dppe)(CH3)](9) and [Fe(η4-C5H6)(dppe)(CO)](8). The latter product is formed exclusively by exo attack on the cyclopentadienyl ligand as evidenced by carrying out the reduction with LiAlD4. The disproportionation of (2) in toluene to give [{Fe(η5-C5H5)(CO)H}2(µ-dppe)](12) and its subsequent thermal and photochemical elimination of dihydrogen has been studied. In contrast, in tetrahydrofuran solutions, (2) disproportionates to (9)via(4). The thermal migration of hydrogen from (2) to produce (8) has been studied. The use of [Fe(η5-C5H5)(dppe)(CO)D](3) has shown this migration to be endo first-order and intramolecular with a kinetic isotope effect close to unity.

Back to tab navigation

Article type: Paper
DOI: 10.1039/DT9840000701
Citation: J. Chem. Soc., Dalton Trans., 1984,0, 701-709

  •   Request permissions

    Carbon monoxide reduction. [Fe(η5-C5H5)(Ph2PCH2CH2PPh2)(CO)H]: reactions and formation by reduction of the complex [Fe(η5-C5H5)(Ph2PCH2CH2PPh2)(CO)]PF6

    S. G. Devies, J. Hibberd, S. J. Simpson, S. E. Thomas and O. Watts, J. Chem. Soc., Dalton Trans., 1984, 0, 701
    DOI: 10.1039/DT9840000701

Search articles by author