Heating a solution of the isomerized (butadiene)(alkoxycarbene)iron complexes [C 4 H 6 (CO) 2 -FeC(OC 2 H 5 )Ar] (1, Ar ) o-CH 3 C 6 H 4 ; 2, Ar ) p-CF 3 C 6 H 4 ) in benzene in a sealed tube at 70-80 °C for 70-72 h gave the H-migrating pyrolytic productsThe isomerized (limonene)(alkoxycarbene)iron complex [η 3 -C 10 H 16 (CO) 2 -FeC(OC 2 H 5 )C 6 H 5 ] (9) was thermally decomposed to produce the η 4 cyclic olefin coordinated tricarbonyliron complex [{η 4 -C 10 H 15 CH(OC 2 H 5 )C 6 H 5 }Fe(CO) 3 ] (23). Interestingly, the thermolysis of the (limonene)(alkoxycarbene)iron complex [η 4 -C 10 H 16 (CO) 2 FeC(OC 2 H 5 )C 6 H 4 CH 3o] (10) can also give the analogous cyclic olefin coordinated tricarbonyliron complex [{η 4 -C 10 H 15 CH(OC 2 H 5 )C 6 H 4 CH 3 -o}Fe(CO) 3 ] (24). The thermolysis of the isomerized 1,5-cyclooctadiene (trimethylsiloxy)carbene iron complex [(CO) 2 Fe{η 6 -p-C 6 H 5 C 6 H 4 C(OSiMe 3 )C 8 H 12 }] (11) yields 9-aryl-9-(trimethylsiloxy)bicyclo[4.2.1]non-2-ene, [p-C 6 H 5 C 6 H 4 C-{OSi(CH 3 ) 3 }C 8 H 12 ] (25). The thermolyses of the isomerized products of the (cyclooctatetraene)(ethoxycarbene)iron complexes [η 3 -C 8 H 8 (CO) 2 FeC(OC 2 H 5 )Ar] (12, Ar ) o-CH 3 C 6 H 4 ; 13, Ar ) C 6 H 5 ) and [η 4 -C 8 H 8 (CO) 2 FeC(OC 2 H 5 )C 6 H 4 CH 3 -p] (14) produced the head-bridged cyclooctatriene derivatives [C 8 H 8 C(OC 2 H 5 )C 6 H 4 CH 3 -o] (26) and [C 8 H 7 (OC 2 H 5 )C(H)Ar] (27, Ar ) C 6 H 5 ; 28, Ar ) p-CH 3 C 6 H 4 ), respectively, via C-C bond formation or ethoxy migration. The structures of compounds 15-17, 20, 23, 25, 26, and 28 were established by X-ray diffraction studies.
The reactions of [μ-(1−3-η):(4−7-η)-cycloheptatrienyl]tricarbonylirontricarbonylmanganese,
[MnFe{μ-(1−3-η):(4−7-η)-C7H7}(CO)6] (1) with 2 molar equiv of aryllithium reagent, ArLi
(Ar = C6H5, o-, m-, p-CH3C6H4), in ether at low temperature gave acylmetalate intermediates,
followed by alkylation with Et3OBF4 in aqueous solution at 0 °C to afford the four novel
ring-opened olefin-coordinated tricarbonylirontricarbonylmanganese complexes [MnFe{C8H7(OC2H5)Ar}(CO)6] (3, Ar = C6H5; 4, Ar = o-CH3C6H4; 5, Ar = m-CH3C6H4; 6, Ar = p-CH3C6H4).
Analogous reactions of [μ-(1−3-η):(4−7-η)-cycloheptatrienyl]tricarbonylirontricarbonylrhenium,
[ReFe{μ-(1−3-η):(4−7-η)-C7H7)}(CO)6] (2), with ArLi (Ar = C6H5, o-, m-CH3C6H4, p-CF3C6H4)
gave the corresponding products [ReFe{C8H7(OC2H5)Ar}(CO)6] (7, Ar = C6H5; 8, Ar =
o-CH3C6H4; 9, Ar = m-CH3C6H4; 10, Ar = p-CF3C6H4). The structures of 4 and 10 have been
established by single-crystal X-ray diffraction studies.
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