The reaction of a cationic carbyne complex of manganese,
[η-C5H5(CO)2Mn⋮CC6H5]BBr4
(1), with the reactive salt
[Et3NH][(μ-CO)(μ-n-C4H9S)Fe2(CO)6]
(3) in THF at low temperature
gave the dimetal bridging carbene complex
[MnFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)]
(8) and
[Fe(CO)3(n-C4H9S)]2
(7). 1 reacted with
[Et3NH][(μ-CO)(μ-C6H5S)Fe2(CO)6]
(4) to give the
bridging carbene complex
[MnFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)]
(11) and the manganese
phenylthiocarbene complex
[η-C5H5(CO)2MnC(C6H5S)C6H5]
(12), besides
[Fe(CO)3C6H5S]2
(10). 1 also reacted with
[Et3NH][(μ-CO)(μ-p-CH3C6H4S)Fe2(CO)6]
(5) to yield
[Fe(CO)3(p-CH3C6H4S)]2
(13) and the bridging carbene complex
[MnFe{μ-C(p-CH3C6H4S)C6H5}(CO)5(η-C5H5)] (14). Analogous
reactions of the cationic rhenium carbyne complex
[η-C5H5(CO)2Re⋮CC6H5]BBr4 (2)
with 3 and 4 gave the corresponding bridging
carbene complexes
[ReFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)]
(16) and
[ReFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)]
(17)
and the phenylthiocarbene complex
[η-C5H5(CO)2ReC(C6H5S)C6H5]
(18), respectively. The
structures of 8, 11, 12,
16, and 18 have been 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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