The reactions and photochemistry of iron and nickel atoms and dimers with small hydrocarbons have been investigated in an argon matrix at 15 K using Fourier transform infrared spectroscopy.
Atomic iron was found to interact with an acetylenic hydrogen in the first example of a transition metal hydrogen-bonding to an alkyne. With UV photolysis this complex rearranged to ethynyliron hydride, HFeC$\sb{2}$H. At higher iron concentrations a $\pi$-coordinated diiron adduct Fe$\sb{2}$(C$\sb{2}$H$\sb{2}$) was formed.
Atomic nickel formed a $\pi$ complex with acetylene which photorearranged with $\lambda \geq 400$ nm irradiation to nickel vinylidene, NiCCH$\sb{2}$. Photoreversibility was demonstrated with UV irradiation. A dinickel acetylene adduct analogous to Fe$\sb{2}$(C$\sb{2}$H$\sb{2}$) was formed at higher nickel concentrations.
In reactions between nickel and ethylene oxide, activation of the C-O bond by atomic nickel resulted in formation of the first unligated nickel oxometallacycle, nickelaoxetane. Upon irradiation with $\lambda \geq 500$ nm this metallacycle underwent two metathesis pathways. One pathway produced an ethylene nickel oxide $\pi$ complex NiO(C$\sb{2}$H$\sb{4}$) which subsequently rearranged to vinylnickel hydroxide, C$\sb{2}$H$\sb{3}$NiOH, with UV photolysis. Another metathesis route resulted in a methylenenickel formaldehyde $\pi$ complex, CH$\sb{2}$Ni(H$\sb{2}$CO), which rearranged upon $\lambda \geq 400$ nm irradiation to hydridonickelmethyl carbonyl, HNiCH$\sb{3}$(CO) decomposed to methane and nickel carbonyl with UV photolysis.
In studies of nickel with cyclopropane in an argon matrix, atomic nickel inserted into a C-C bond of cyclopropane to form nickelacyclobutane. Irradiation with $\lambda \geq 500$ nm caused metathesis of this metallacycle and formation of methylenenickel ethylene $\pi$ complex, CH$\sb{2}$Ni(C$\sb{2}$H$\sb{4}$). CH$\sb{2}$Ni(C$\sb{2}$H$\sb{4}$) rearranged to vinylnickelmethyl, C$\sb{2}$H$\sb{3}$NiCH$\sb{3}$, which decomposed and released methane upon extended UV photolysis.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/16078 |
| Date | January 1987 |
| Creators | KLINE, ELLEN SUE |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | application/pdf |
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