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- W2052117432 abstract "Abstract The synthesis, structure and reactions of rhenium(III)η1-acyl complexes bearing a cyclopentadienyl (Cp) or a pentamethylcyclopentadienyl (Cp*) ligand are described. Oxidation of the rhenium(I) acyl complexLi[CpRe(CO)2(η1-PhCO)] (1) with one equivalent of PhICl2 affords the rhenium(III) acyl complex trans-CpRe(CO)2(η1-PhCO)Cl (trans-2a). The diphenylcarbene complex Cp(CO)2Re CPh2 (3) is also formed in this reaction. Similarly, oxidation of1 with Br2 givescis/trans-CpRe(CO)2(η1-PhCO)Br(cis/trans-2b), which can also be obtained from the alkoxycarbene complex Cp(CO)2Re C(OEt)Ph (4) with one equivalent of Br2. Oxidation ofLi[Cp*Re(CO)2(η1-PhCO)] (5) with one equivalent of PhlCl2, Br2 or I2 affords selectively the rhenium(III) acyl complexescis/trans-Cp*Re(CO)2(η1-PhCO)X(X Cl I) [cis/trans-(6a–6c)]. Cleavage of the Re Cacyl bond oftrans-2a with PhICl2 and ofcis/trans-2b with Br2 offers a convenient way to the rhenium(III) dihalo complexescis/trans-CpRe(CO)2Cl2 (cis/trans-7a) andcis/trans-CpRe(CO)2Br2 (cis/trans-7b) respectively. Reduction ofcis/trans-7a with sodium/amalgam gives in the presence of RNC, the rhenium(I) isonitrile complexes CpRe(CO)2(CNR) (8:R Et;9:R 10:R 1Bu). Oxidation of8–10 with one equivalent of bromine leads selectively to the rhenium(III) isonitrile complexes [trans-CpRe(CO)2(CNR)Br]Br (11:R = Et;12:R -iPr;13:R =tBu). The crystal structure of the acyl complextrans-2b and the carbonyl complex [Cp2*Re2(CO)4(μ-Br)][Re2(μ-Br)3(CO)6] (14) are described, complex14 being formed by the thermal decomposition ofcis/trans-6b." @default.
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- W2052117432 date "1996-11-01" @default.
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- W2052117432 title "Half-sandwich rhenium(III) acyl complexes: synthesis, structure and conversion to rhenium(I) and rhenium(III) isonitrile complexes" @default.
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- W2052117432 doi "https://doi.org/10.1016/s0022-328x(96)06401-7" @default.
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