Photolytic Preparation Of (benzylideneacetone)carbonylphosphineiron(0) Complexes. The Molecular Structures Of Fe(co)2(pet3)(bda) And Fe(co)2(pphme2)(bda) (bda Benzylideneacetone)

The (benzylideneacetone) carbonylphosphine iron(0) complexes, Fe(CO)2L(bda), Fe(CO)L′2(bda) and Fe(CO)(dpe)(bda)(L = PEt3, PPhMe2, Me; L′ = PPhMe2, PPh2Me; dpe = [Ph2P(CH2)]2) have been prepared by irradiating the corresponding tetracarbonylmonophosphine iron(0), tricarbonyldiphosphine iron(0) or tricabonyl-1,2-bis (diphenylphosphine)ethane iron(0) complexes in benzene in the presence of benzylideneacetone. The X-ray crystal structures of the complexes with L = PEt3 (A) and PPhMe2 (B) have been determined, and show that the Fe atom adopts a distorted octahedral coordinated geometry in which three of the sites are occupied by the bda ligand. The bond parameters in the bda ligand suggest that this coordinated group is intermediate between its ground and first excited states. The complex Fe(CO)2(PEt3(bda) crystallises in the monoclinic space group P2l/c with a 10.203(3), b 12.964(4), c 16.960(6) Å, β 120.00(2)°, and Z = 4. The structure was solved by a combination of Patterson and Fourier diffence techniques and refined by blocked full matrix least squares to R = 0.035 for 3351 unique observed diffratometer data. The complex Fe(CO)2(PPhMe2)(bda) also crystallises in space group P2l/c, with a 8.134(3), b 21.394(8), c 11.658(5) Å, β 108.18(2)° and Z = 4. The structure was solved and refined as above to R = 0.036 for 3498 diffractometer data. The IR and 1H NMR data for all the complexes studied agree with the observed structures. © 1983.2561111124Otsuka, Yoshida, Nakanima, (1967) Inorg. Chem., 6, p. 20tom Dieck, Bock, (1968) J. Chem. Soc. Chem. Commun., p. 678Brodie, Johnson, Josty, Lewis, Some ?-hetero-1,3-diene complexes of iron carbonyl (1972) Journal of the Chemical Society, Dalton Transactions, p. 2031Liebfritz, tom Dieck, Intramolekularer ligandenaustausch in einkernigen heterodien-eisentricarbonylkomplexen (1976) Journal of Organometallic Chemistry, 10, p. 255Vessieres, Dixneuf, (1974) Tetrahedron Lett., p. 1499Vessieres, Dixneuf, (1976) J. Organomet. Chem., 108, p. C5Howell, Johnson, Lewis, (1972) J. Organomet. Chem., 39, p. 326Johnson, Lewis, Stephenson, Vichi, Preparation and reactions of triphenylphosphine and triphenyl phosphite complexes of (benzylideneacetone)dicarbonyliron(0) (1978) Journal of the Chemical Society, Dalton Transactions, p. 369Henderson, Streuli, (1960) J. Amer. Chem. Soc., 82, p. 5791Tolman, (1977) Chem. Revs., 77, p. 313Pearson, Raithby, Diene?metal ? bonding. Some unexpected effects of Group 5 donor ligands on carbon-13 nuclear magnetic resonance parameters and X-ray crystal structures (1981) Journal of the Chemical Society, Dalton Transactions, p. 884Kruger, Barnett, Brauer, Koerner von Gustorf, Grevels, (1978) The Organic Chemistry of Iron, , I. Fischler, Academic Press, New York, ch. 1 and refs. therein;Pearson, Raithby, Organoiron complexes in organic synthesis. Part 4. Direct ring connection between highly substituted centres. A potential approach to trichothecane synthesis (1980) Journal of the Chemical Society, Perkin Transactions 1, p. 395Churchill, Chang, (1977) Inorg. Chem., 129, p. 105Mills, Robinson, (1960) Proc. Chem. Soc., p. 421Mills, Robinson, Studies of some carbon compounds of the transition metals. IV. The structure of butadiene irontricarbonyl (1963) Acta Crystallographica, 16, p. 758Chaudari, Pauson, (1966) J. Organomet. Chem., 5, p. 73Edwards, Howell, Johnson, Lewis, (1974) J. Chem. Soc., Dalton Trans., p. 2107(1974) International Tables for X-ray Crystallography, 4. , Kynoch Press, BirminghamSHELX 76, G M Sheldrick (1976) A molecular structure determination program package, , Cambridg