Synthesis and characterization of perhalogenated triphenylphosphine-cymantrenes [(C5X5)Mn(CO)2(PPh3)] (X = F, Cl, Br) and [(C5HI4)Mn(CO)2(PPh3)]

•A complete series [(C5X5-nHn)Mn(CO)2(PPh3)] (X=Cl, Br; n=0–4) was prepared.•All [(C5I5-nHn)Mn(CO)2(PPh3)] (n=1–4) could be prepared.•All [(C5F5-n-mHnClm)Mn(CO)2(PPh3)] (m+n=2–4;m=0–2) were prepared.•All compounds were characterized by spectroscopic methods and X-ray diffraction Photolysis of the mo...

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Published inJournal of organometallic chemistry Vol. 943; p. 121833
Main Authors Klein-Heßling, Christian, Blockhaus, Tobias, Sünkel, Karlheinz
Format Journal Article
LanguageEnglish
Published Elsevier B.V 21.06.2021
Subjects
Cymantrene
Perhalocyclopentadienyl complexes
Photolysis
Cymantrene
Photolysis
Perhalocyclopentadienyl complexes
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Summary:•A complete series [(C5X5-nHn)Mn(CO)2(PPh3)] (X=Cl, Br; n=0–4) was prepared.•All [(C5I5-nHn)Mn(CO)2(PPh3)] (n=1–4) could be prepared.•All [(C5F5-n-mHnClm)Mn(CO)2(PPh3)] (m+n=2–4;m=0–2) were prepared.•All compounds were characterized by spectroscopic methods and X-ray diffraction Photolysis of the monohalocymantrenes [(C5H4X)Mn(CO)3] (X= F, Cl, Br, I) in the presence of triphenylphosphine yields the corresponding dicarbonyl complexes [(C5H4X)Mn(CO)2(PPh3)]. Stepwise metalation and electrophilic quench with (PhSO2)2NF, C2Cl6, C2HBr5 or I2, respectively leads to [(C5H2F3)Mn(CO)2(PPh3)], [(C5X5)Mn(CO)2(PPh3)] (X= Cl, Br) and [(C5HI4)Mn(CO)2(PPh3)]. Further fluorination or iodination leads only to decomposition. However, lithiation of [(C5H2F3)Mn(CO)2(PPh3)] is possible and electrophilic quench with C2Cl6 leads finally to [(C5F3Cl2)Mn(CO)2(PPh3)]. The crystal structures of the tetra- and pentasubstituted compounds are reported. [Display omitted]
ISSN:0022-328X
1872-8561
DOI:10.1016/j.jorganchem.2021.121833