| Summary: | 碩士 === 國立臺灣師範大學 === 化學學系 === 85 ===
The reactions of [Et4N]2[(μ3-E)Fe3(CO)9] with propargyl bromide in CH2CI2 afford novel heterotetranuclear metal-(acylallenyl) complexes, [Et4N][(μ3-E)Fe3(CO)9(μ3η1:η1:η3-C(O)C(H)=C=CH2)](E=Se, Ia; E=Te, Ib), respectively.
When Ia is treated with [Cu(CH3CN)4]BF4, (μ3-Se)Fe3(CO)9(μ3-C(CH3)=CH)(IIa) and SeFe2(CO)6(μ3-C(CH3)=CHC(O))(III) are obtained.Whereas Ib reacts with [Cu(CH3CN)4]BF4，Te2Fe3(CO)9 is produced. Further reaftion of Ia with CH3SO3CF3 produces two rotational isomeers (E and Z forms), (μ3-Se)Fe3(CO)9(μ3-η2:η1:η3-C(OCH3)CH=C=CH2) (IVa1,IVa2). However, the reaction of Ib with CH3SO3CF3 forms (μ3-Te)Fe3(CO)9(μ3-η2:η1:η3-C(OCH3)CH=C=CH2) (IVb), with only one conformation (Z form).
The treatments of K2TeO3.H2O with Mn2(CO)10 in methanol, in different ratios, produce [Te4Mn3(CO)10]-(VII), [Te2Mn3(CO)9]2- (VIII), and [Te2Mn4(CO)12]2- (IX), respectively. The reaction of [Te2Mn4(CO)12]2- with CH3SO3CF3 forms the methylated product, [Te2Mn4(CO)12Mn(CO)4Te(CH3)2]- (X).
Complexes I-X are fully structurally characterized by X-ray analysis and spectroscopy methods. The reactivity and structural transformations of three new clusters are also studied and described.
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