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Acyl-Functionalized Molybdenum Compounds [(η3-C3H5)(η5-Cp)Mo(CO)2]: An Experimental Study Including the X-ray Structure of a Rare endo Conformer
Year: 2014
Type of publication: článek v odborném periodiku
Name of source: European Journal of Inorganic Chemistry
Publisher name: Wiley-VCH
Place: Weinheim
Page from-to: 5895-5907
Titles:
Language Name Abstract Keywords
cze Sloučeniny molybdenu substituované acylovou skupinou [(η3-C3H5)(η5-Cp)Mo(CO)2]: experimentální studie zahrnující RTG-sttrukturu endo-konformeru Série nových sloučeniny molybdenu substituovaných acylovou skupinou [(η3-C3H5)(η5-C5H4COR)Mo(CO)2] byla úspěšně syntetizována, krystalograficky charakterizována a použita pro studium vztahu mezi reaktivitou a elektronickými vlastnostmi dané organokovové sloučeniny. RTG studie odhalila, že [(η3-C3H5)(η5-C5H4COCF3)Mo(CO)2] tvoří v pevné fázi neobvyklý endo-konformer, který byl pro tento typ sloučeniny pozorován v krystalové mřížce. Dále bylo ukázáno, že deriváty nesoucí velmi silnou elektronově akceptornískupinu(-CHO, -COCF3) poskytují jiný produkt protonační reakce než nesubstituovaný analog. Tato studie dále ukázala vysokou reaktivitu fomylového derivátu [(η3-C3H5)(η5-C5H4CHO)Mo(CO)2]. Sendvičové komplexy; molybden; efekty ligandu; IR spektroskopie; Ramanova spektroskopie
eng Acyl-Functionalized Molybdenum Compounds [(η3-C3H5)(η5-Cp)Mo(CO)2]: An Experimental Study Including the X-ray Structure of a Rare endo Conformer A series of new acyl-functionalized molybdenum(II) complexes [(η3-C3H5)(η5-C5H4COR)Mo(CO)2] have been successfully synthesized and crystallographically characterized, and the relationship between the reactivity and electronic properties of these organometallic compounds has been studied in detail. The X-ray analysis revealed [(η3-C3H5)(η5-C5H4COCF3)Mo(CO)2] to exist as a rare endo conformer, the first time that this structure has been observed in the crystal lattice of a [(η3-C3H5)(η5-Cp′)Mo(CO)2] (Cp′ = substituted Cp) complex without any disorder. It has also been demonstrated that the derivatives bearing very strong electron-withdrawing acyl groups (e.g., -CHO, -COCF3) show different outcomes in the protonation reactions compared with the parent cyclopentadienyl compound or derivatives bearing less electron-withdrawing groups (e.g., -COMe, -COPh). This study has also revealed the increased reactivity of the formyl derivative [(η3-C3H5)(η5-C5H4CHO)Mo(CO)2] towards aromatic amines. An IR spectroscopic analysis revealed that the aldimine-functionalized products formed very quickly even under the mild conditions that fulfill the basic rules of click chemistry. Sandwich complexes; Molybdenum; Ligand effects; IR spectroscopy; Raman spectroscopy

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