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Comparative Photochemistry of Tricarbonyl(η5-cyclopentadienyl)methyl- and -ethyl-molybdenum and -tungsten in Poly(vinyl chloride) Film Matrices at 12-298 K

DOI: 10.1039/DT9840000761

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 761 - 770 (1984)

Update date:2022-08-24

Topics:

Authors:

Hooker, Richard H.Hooker, Richard H.

Rest, Antony J.Rest, Antony J.

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Article abstract of DOI:10.1039/DT9840000761

The photoreactions of 5-C5H5)(CO)3(CH3)> and 5-C5H5)(CO)3(C2H5)> complexes (M = Mo or W) in poly(vinyl chloride) (pvc) film matrices over a wide temperature range have been monitored using i.r. spectroscopy.At 298 K the methyl complexes dealkylate on irradiation (λ > 300 nm) to form 5-C5H5)(CO)3Cl>, 5-C5H5)(CO)3H>, and 5-C5H5)2(CO)6>.Photolysis at 12 K leads primarily to the formation of 5-C5H5)(CO)2(CH3)>.In the case of molybdenum, M-CH3 bond cleavage also occurs at 12 K and the complexes 5-C5H5)(CO)3Cl> and 5-C5H5)(CO)3H> are generated on warming the matrices.Photolysis of 5-C5H5)(CO)3(C2H5)> at 12 K proceeds with the formation of 5-C5H5)(CO)2(C2H5)> which rearranges photochemically or thermally to form trans-5-C5H5)(CO)2(C2H4)H>.The cis-ethylene-hydride complex is also observed for tungsten at temperatures below ca. 50 K.At 298 K, photolysis of 5-C5H5)(CO)3(C2H5)> leads directly to trans-5-C5H5)(CO)2(C2H4)H> which reacts further to form 5-C5H5)(CO)3H>, 5-C5H5)(C0)2(C2H4)Cl>, 5-C5H5)(CO)3Cl>, and 5-C5H5)2(CO)6>.However, on photolysis of 5-C5H5)(CO)3(C2H5)> at 298 K the main product observed is with trace amounts of 5-C5H5)(CO)3H>, 5-C5H5)(CO)3Cl>, and 5-C5H5)2(CO)6>.

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Product name:CYCLOPENTADIENYLMOLYBDENUM(II) TRICARBO&

Cas No:12128-23-3

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