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- W1999006970 abstract "UV-Vis and infrared spectroscopic evidence, including 13CO labelling and energy-factored force-field fitting, is presented which shows that photolysis of(η5-C5H5)Cr(CO3)CH3 at high dilution in frozen gas matrices (Ar, CH4, N2, and CO) and poly(vinyl chloride) films at ca. 12 K affords the α-elimination product, trans-η(5-C5H5)Cr(CO)2(CH2)H, via the 16-electron species (η5-C5H5)Cr(CO)2CH3. These reactions are thermally reversible at temperatures as low as 30 K with conversion of (η5-C5H5)Cr(CO)2(CH2)H to (η5-C5H5)Cr(CO)2(L)CH3 complexes (L = CO and tetrahydrofuran) in poly(vinyl chloride) films. Irradiation of (η5-C5H5)Cr(CO)3CH3 in poly(vinyl chloride) films at 298 K yielded the dimer (η5-C5H5)2Cr2(CO))6 analogously to the solution photochemistry. The results are discussed in relation to the occurrence of α-H elimination reactions in general and the reactions of (η5-C5H5(Cr(CO)3CH3 in particular. It is suggested that the formation of the dimer (η5-C5H5)2Cr2(CO)6 in solution arises not from initial CrCH3 bond cleavage or α-H elimination but from reactions of (η5-C5H5)Cr(CO)2CH3 or (η5-C5H5)Cr(CO)2(solvent)CH3 species with unreacted (η5-C5H5Cr(CO)3CH3." @default.
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- W1999006970 date "1974-01-01" @default.
- W1999006970 modified "2023-09-26" @default.
- W1999006970 title "Transition metal—carbon σ-bond scission" @default.
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- W1999006970 doi "https://doi.org/10.1016/s0022-328x(00)92174-0" @default.
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