Unexpected reactions of (cyclooctatetraene) diiron hexacarbonyl with aryllithium reagents: Crystal structures of [(CO)3Fe(1–4-η:5–7-ηC8H9)(CO)2Fe (COC6H5)] and [(CO)3Fe(1–4-η:5–8-η-C8 H8)(CO)2FeC(OC2H5)C6H5]

doi:10.1016/S0022-328X(96)06815-5

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Unexpected reactions of (cyclooctatetraene) diiron hexacarbonyl with aryllithium reagents: Crystal structures of [(CO)3Fe(1–4-η:5–7-ηC8H9)(CO)2Fe (COC6H5)] and [(CO)3Fe(1–4-η:5–8-η-C8 H8)(CO)2FeC(OC2H5)C6H5]

Yongfei Yu, Jie Sun, Jiabiao Chen

Apr 15, 1997

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Journal

Journal of Organometallic Chemistry

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Abstract

Abstract The reaction of (cyclooctatetraene)diiron hexacarbonyl (1) with aryllithium reagents ArLi (Ar = C6H5, o-, m-, p-CH3C6H4, p-CH3OC6H4 in ether at low temperature afforded acylmetalate intermediates. Subsequent alkylation with Et3OBF4 in aqueous solution at 0°C gave the (8,8-dihydro-1-4-η:5-7-η-cyclooctatrienyl) tricarbonylirondicarbonyl(arylformacyl)iron complexes [(CO)3Fe(1–4-η:5–7-η-C8H9) (CO)2Fe(COAr)] (2a-e) (2a, Ar = C6H5; 2b, Ar = o-CH3C6H4; 2c, Ar = m-CH3C6H4; 2d, Ar = p-CH3C6H4; 2e, Ar = p-CH3OC6H4) and (1–4-η:5–8-η-cyclooctatetraene)tricarbonylirondicarbonyl [ethoxy(aryl)carbene]iron complexes [(CO)3Fe(1–4-η:5–8-η-C8H8) (CO)2FeC(OC2H5)Ar] (3a-e) (3a, Ar = C6H5; 3b, Ar = o-CH3C6H4; 3c, Ar = m-CH3C6H4; 3d, Ar = p-CH3C6H4; 3e, Ar = p-CH3OC6H4). The structures of 2a and 3a have been established by X-ray diffraction studies, which indicate that the Fe(CO)3 unit and the (CO)2Fe(COC6H5 moiety in 2a and the (CO)2FeC(OC2H5)C6H5 moiety in 3a are on opposite sides of the cyclooctatetraene ring.

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