Reactions of RSe− (R = Me,Ph) Groups in [RSeFe(CO)4I and [RSeCr(CO)5−] |
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Authors: | Wen-Feng Liaw Chen-Ju Liu Chia-Huei Lai |
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Abstract: | The anionic [MeSeFe(CO)4] and [MeSeCr(CO)5] complexes were synthesized by reaction of [PPN][HFe(CO)4] and [PPN][HCr(CO)5] with MeSeSeMe respectively via nucleophilic cleavage of the Se-Se bond. The ease of cleavage of the Se-Se bond follows the nucleophilic strength of metal-hydride complexes. Methylation of [RSeCr(CO)5?] by the soft alkylating agent MeI resulted in the formation of neutral (MeSeMe)Cr(CO)5 in THF at 0°C. In contrast, the [ICr(CO)5?] was isolated at ambient temperature. Reaction of [MeSeFe(CO)4?] or [MeSeCr(CO)5?] with HBF4 yielded (CO)3Fc(μ-SeMe)2Fe(CO)3 dimer and anionic [(CO )5Cr (μ-SeMe)Cr(CO)5?] respectively, and no neutral (HSeMe)Fe(CO)4 and (HSeMe)Cr(CO)5 were detected spectrally (IR) even at low temperature. Reaction of NOBF4 or [Ph3C][BF4] and [MeSeCr(CO)5?] resulted in the neutral monodentate (MeSeSeMe)Cr(CO)5 complex. Addition of 1 equiv CpFe(CO)2I to 2 equiv [MeSeCr(CO)5?] gave CpFe(CO)2(SeMe) and the anionic [(CO)5Cr(μ-SeMe)Cr(CO)5?] in THF at ambient temperature. |
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Keywords: | Alkylselenate Selenoether Monodentate |
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