TY - JOUR
T1 - Structural investigations on new iron-acyl derivatives of B(C6F5)(3)
AU - Anderson, G D W
AU - Boys, O J
AU - Cowley, A R
AU - Green, J C
AU - Green, M L H
AU - Llewellyn, S A
AU - von Beckh, C M
AU - Pascu, Sofia I
AU - Vei, I C
PY - 2004
Y1 - 2004
N2 - Reactions between [Fe(eta-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)(3) give new complexes [Fe(eta-C5H5){MeCOB(C6F5)(3)}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCY3 (10), CO (11), where B(C6F5)(3) coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(eta-C5H5){HOB(C6F5)(3)}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the sigma than the pi system. Both effects lead to a lengthening of the acyl C-O bond thus pi populations cannot be inferred from the distance changes.
AB - Reactions between [Fe(eta-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)(3) give new complexes [Fe(eta-C5H5){MeCOB(C6F5)(3)}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCY3 (10), CO (11), where B(C6F5)(3) coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(eta-C5H5){HOB(C6F5)(3)}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the sigma than the pi system. Both effects lead to a lengthening of the acyl C-O bond thus pi populations cannot be inferred from the distance changes.
UR - http://dx.doi.org/10.1016/j.jorganchem.2004.07.013
U2 - 10.1016/j.jorganchem.2004.07.013
DO - 10.1016/j.jorganchem.2004.07.013
M3 - Article
SN - 0022-328X
VL - 689
SP - 4407
EP - 4419
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 24
ER -