Low-temperature matrix photochemistry of (1,3-diene)tricarbonyliron complexes

Ellerhorst, Gabriele; Gerhartz, Wolfgang; Grevels, Friedrich‐Wilhelm

doi:10.1021/ic50203a015

Cited by 33 publications

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“…This reaction may be compared to loss of ethene from WCp2(C2H4)' or the partial decoordination of butadiene in Fe(7/-C4H6)(CO)3. 43 As expected, 7 was replaced in reactive CO or N2 matrices by 2 and 8, respectively. To our surprise, there was no evidence for CO loss as a competing pathway (cf.…”

Section: Discussionsupporting

confidence: 61%

Photochemical studies of rhenium .eta.-cyclopentadienyl complexes in matrixes and in solution: detection of rhenocene and mechanisms of hydrogen transfer

Chetwynd-Talbot¹,

Grebenik²,

Perutz³

et al. 1983

Inorg. Chem.

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Section: Discussionsupporting

confidence: 61%

Photochemical studies of rhenium .eta.-cyclopentadienyl complexes in matrixes and in solution: detection of rhenocene and mechanisms of hydrogen transfer

Chetwynd-Talbot¹,

Grebenik²,

Perutz³

et al. 1983

Inorg. Chem.

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“…The analogous iron radical (vco 2 004 and 1938 cm-') has been observed by Turner and cow o r k e r ~, ~ and the bands observed here are of similar frequencies and relative intensities to those of the iron radical and to those of matrix-isolated [Fe(q4-C4H6)(Co),] (vco 2 009 and 1 934 cm-' in argon). 23 The assignment is also supported by the fact that on annealing both the bridged and non-bridged isomers are produced on recombination of the radicals.…”

Section: (A) Photolysis Of [Ru(~~mentioning

confidence: 91%

Photochemistry of some iron and ruthenium (η⁵-cyclopentadienyl) carbonyl dimers in frozen gas matrices at ca. 12 K

Bloyce¹,

Campen²,

Hooker³

et al. 1990

J. Chem. Soc., Dalton Trans.

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The photochemistry of [M,(q5-C,H,) ,(CO),][M = Fe, (1); or Ru, (2)] and [CH,{(q5-C,H,)M(C0), },] [M = Fe, (5); or Ru, ( 6)] has been studied in frozen-gas matrices (Ar, CH, , and N, ) at ca. 12 K and that of (2) in poly(viny1 chloride) (pvc) films at ca. 12 K. Low-energy photolysis of compounds (1) and (2) was found to induce opening of trans-carbonyl-bridged species affording terminal carbonyl species. Photolyses into the electronic absorption band maxima of these new terminal-carbonyl species yielded 17-electron radical species [ M(q5-C,H,) (CO),]' as well as small amounts of triply carbonyl-bridged species, [M,(q5-C5H5),(p-C0),1. At the corresponding maxima of trans-carbonyl-bridged complexes (1 ) and ( 2) photolysis yielded the triply-carbonyl-bridged species directly. Photolysis of (5), which is exclusively bridging and is constrained by the methylene linkage between the rings to be in a cis conformation, at a range of wavelengths showed no evidence for carbonyl-bridge opening. At its electronic absorption maxima photolysis resulted in carbonyl ejection and formation of a new species whose spectrum is consistent with its having three terminal carbonyl groups and an Fe-Fe double bond. Photolysis of compound (6) which exists in a cis-terminal conformation also resulted in carbonyl loss and formation of a species similar to that observed for (5). These results are discussed in terms of their relationship to previous photochemical studies of (1) and ( 2) and an overall model for the photochemical behaviour of (1) and (2) is presented.

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“…[Fe(q4-C4H6)(CO),] (vco at 2 009 and 1 944 cm-'). 19 One of the possible contenders [(2)-(5); Scheme 11, structure (4), can be eliminated because the instantaneous structure has an q2-cot ligand, and additionally two conformations would be expected to be frozen out at 12 K, cf. the two conformations of the acetyl ligand frozen out at 12 K for [Fe(qs-CsHS)(CO),-(COCH,)] and for [ Mn(CO),(COCH3)].24*2s The formation of two of the other possible contenders, (2) and (3), would require considerable changes in the conformation of the cot ligand together with a shift of the [Fe(CO),] fragment with respect to the ring.…”

Section: Discussionmentioning

confidence: 99%

Photochemistry of tricarbonyl(η⁴-cyclo-octatetraene)iron in a methane matrix at 12 K. Infrared spectroscopic evidence for photoisomerisation and carbon monoxide ejection reactions

Hitam¹,

Narayanaswamy²,

Rest³

1983

J. Chem. Soc., Dalton Trans.

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Fourier-transform infrared spectroscopic evidence, including 3C0 labelling and energy-factored CO force-field fitting, is presented to show that photolysis of [Fe(' tub '-q4-C8H,)(C0)3] in a CH4 matrix at 12 K leads to the formation of a [Fe(' chair'-q4-C8Ha)(C0)3] species via the [Fe(q2-C,H8)(C0)3] intermediate. An additional photoproduct is the co-ordinatively unsaturated species [ Fe(q4-C8H8) (CO),] formed by photoelimination of a CO ligand. The results are related to the fluxional behaviour of [Fe(q4-C8H,) (CO)3] in solution.A single-crystal X-ray diffraction study of tricarbonyl(cyc1o-0ctatetraene)iron showed that the [Fe(CO),] fragment, which has C, symmetry, is bonded to a 1,3-diene fragment of the cyclo-octatetraene (cot) molecule.' There are a number of ways the cot molecule could bind 2-4 (Scheme 1) but the X-ray study and a variety of spectroscopic studies, e.g. infrared and Raman,5 low-temperature 'H n.m.r.,6a7 and Mossbauer: all favour structure (1). This structure is henceforth denoted as [Fe(' tub '-q4-C8H8)(C0),] or [Fe(' tub '-q4-cot)The fluxional behaviour of [Fe(q4-cot)(CO),] in solution and the solid state has been known for many years.' N.m.r. studies ('H and 13C)6*10 are consistent with a rapid interconversion of isomers (6a) * (6b) Fe through 1'2-shifts of (6a) (6b)

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Low-temperature matrix photochemistry of (1,3-diene)tricarbonyliron complexes

Cited by 33 publications

References 0 publications

Photochemical studies of rhenium .eta.-cyclopentadienyl complexes in matrixes and in solution: detection of rhenocene and mechanisms of hydrogen transfer

Photochemical studies of rhenium .eta.-cyclopentadienyl complexes in matrixes and in solution: detection of rhenocene and mechanisms of hydrogen transfer

Photochemistry of some iron and ruthenium (η⁵-cyclopentadienyl) carbonyl dimers in frozen gas matrices at ca. 12 K

Photochemistry of tricarbonyl(η⁴-cyclo-octatetraene)iron in a methane matrix at 12 K. Infrared spectroscopic evidence for photoisomerisation and carbon monoxide ejection reactions

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Low-temperature matrix photochemistry of (1,3-diene)tricarbonyliron complexes

Cited by 33 publications

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Photochemical studies of rhenium .eta.-cyclopentadienyl complexes in matrixes and in solution: detection of rhenocene and mechanisms of hydrogen transfer

Photochemical studies of rhenium .eta.-cyclopentadienyl complexes in matrixes and in solution: detection of rhenocene and mechanisms of hydrogen transfer

Photochemistry of some iron and ruthenium (η5-cyclopentadienyl) carbonyl dimers in frozen gas matrices at ca. 12 K

Photochemistry of tricarbonyl(η4-cyclo-octatetraene)iron in a methane matrix at 12 K. Infrared spectroscopic evidence for photoisomerisation and carbon monoxide ejection reactions

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Photochemistry of some iron and ruthenium (η⁵-cyclopentadienyl) carbonyl dimers in frozen gas matrices at ca. 12 K

Photochemistry of tricarbonyl(η⁴-cyclo-octatetraene)iron in a methane matrix at 12 K. Infrared spectroscopic evidence for photoisomerisation and carbon monoxide ejection reactions