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Oxygen Transfer from Chromyl Chloride to Alkynes and Allene – IR‐Spectroscopic Identification of η 1 ‐Ketene and Cyclopropanone Complexes of O=CrCl 2
Author(s) -
Wistuba Tobias,
Limberg Christian
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199908)1999:8<1335::aid-ejic1335>3.0.co;2-3
Subject(s) - chemistry , ketene , allene , acetylene , photochemistry , electrophile , medicinal chemistry , yield (engineering) , chloride , organic chemistry , catalysis , materials science , metallurgy
Photolytically‐induced reactions of chromyl chloride with acetylene and but‐2‐yne (dimethylacetylene) in low‐temperature argon matrices yield end‐on ketene and dimethylketene complexes of O=CrCl 2 , respectively. The product formation probably results from an electrophilic attack of a Cr=O linkage on the C≡C triple bonds, leading to radical‐like transition states or intermediates, which subsequently rearrange through 1,2‐H or 1,2‐methyl shifts. Consequently, allene is attacked at its central carbon and the allyl radical thus generated undergoes subsequent ring‐closure to give a cyclopropanone complex of O=CrCl 2 .