Photochemistry of metal—metal bonded complexes

Kokkes, Maarten W.; Lange, Wim G. J. de; Stufkens, Derk J.; Oskam, A.

doi:10.1016/0022-328x(85)88053-0

Cited by 43 publications

(29 citation statements)

References 24 publications

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“…In accordance with the complexes [Mn2(CO)~0], [Re2(CO)ao] and [(CO)sM-M'(CO)3(a-diimine)] (M, M' =Mn, Re) [7,29], vs(Mn-Ru) is expected in the frequency region 100-250 cm -1. The rR spectra did not show any strong band in this region which means that the metal-metal bond is hardly affected by the electronic transitions in the visible region.…”

Section: Resonance Raman Spectrasupporting

confidence: 78%

“…The complex will distort in this metal-ligand antibonding (~-*--d,,) excited state and this distortion is reflected in the rR effects for the deformation modes of the a-diimine ligand. A similar effect has been observed for the metal-metal bonded complexes [(CO)sM-M'(CO)3(a-diimine)] (M, M'=Mn, Re) [7].…”

Section: Resonance Raman Spectrasupporting

confidence: 77%

“…Highly coloured complexes are obtained if two carbonyls are substituted by a ligand with a low-lying ~'*-orbital, such as an a-diimine. Best known in this respect are the complexes [MM'(CO)s(ot-diimine)] (M, M' =Mn, Re) [4][5][6][7][8][9]. These complexes are usually very photoreactive and, depending on the relative strengths of the metal-metal and metal-CO bonds, homolytic cleav-age of the metal-metal bond or CO dissociation Occurs. Because of the observed photoreactivity, the lowestenergy absorption band has first been assigned to a ~r~ ~ ~'* (a-diimine) transition [4,10,11].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with α-diimine ligands. X-ray structure of [(CO)5MnRu(Me)(CO)2(σ(N′)-iPr-PyCa)] (iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine)

Nieuwenhuis

Loon

Moraal

et al. 1995

Inorganica Chimica Acta

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Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with alpha-diimine ligands. X-ray structure of [(CO)5Mn-Ru(Me)(CO)2(sigma(N')-iPr-PyCa)](iPr-PyCa = pyridine-2-carbaldehyde-Nisopropylimine) Nieuwenhuis Oskam, A., & Goubitz, K. (1995). Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with alpha-diimine ligands. X-ray structure of [(CO)5Mn-Ru(Me)(CO)2(sigma(N')-iPr-PyCa)](iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine). Inorganica Chimica Acta, 232, 19-25. DOI: 10.1016/0020-1693(94)04360-8 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with t -diimine ligands. X-ray structure of [(CO)sMn-Ru(Me) (CO)a(a(N),a(N') Received 4 July 1994; revised 6 September 1994 AbstractThe synthesis and spectroscopy of the complexes [(CO)sMn-Ru(Me)(CO)2(a-diimine)] (a-diimine=N,N'-diisopropyl-l,4-diaza-l,3-butadiene (iPr-DAB), pyridine-2-carbaldehyde-N-isopropylimine (iPr-PyCa)) are reported. The metal fragments are bonded to each other by an uncommon manganese-ruthenium bond. The single crystal X-ray structure has been determined. The purple crystals of [(CO)sMn-Ru(Me)(CO)2(iPr-PyCa)] are monoclinic, space group P21/n, Z=4, with unit cell dimensions a = 9.6297(7), b = 20.923(1), c = 10.166(1) ~ and fl = 92.190(8) °. The structure refinement converged to R = 0.035 for 3277 observed reflections. Both complexes show a strong, solvatochromic absorption band in the visible region, which is assigned to Ru (d,~)~a-diimine (~-*) transitions. In agreement with this assignment, the Raman spectra show resonance enhancement of Raman intensity for vs(CO) and vs(CN) of the Ru(Me)(CO)2(a-diimine) fragment.

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Section: Resonance Raman Spectrasupporting

confidence: 78%

Section: Resonance Raman Spectrasupporting

confidence: 77%

Section: Introductionmentioning

confidence: 99%

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Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with α-diimine ligands. X-ray structure of [(CO)5MnRu(Me)(CO)2(σ(N′)-iPr-PyCa)] (iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine)

Nieuwenhuis

Loon

Moraal

et al. 1995

Inorganica Chimica Acta

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“…Release of CO has been observed only for the complexes [L,M-Mn(CO)3(a-diimine)] [12,13]; this reaction probably occurs from a low-lying LF state, since it was also observed for the corresponding halide complexes [Mn(X)(CO)3(a-diimine) ] [14]. The homolysis reactions, previously studied in detail for the above-mentioned metal-metal-bonded complexes [L,M-M'(CO)3(a-diimine)] [1][2][3][4][5][6], proceeded with very high quantum yields (0.3-0.9). The radicals [M'(CO)3(a-diimine)]" could be detected by ESR spectroscopy, often without using a spin trap.…”

Section: Introductionmentioning

confidence: 81%

“…complexes can lead to the formation of radicals if the metal-a-diimine moiety is covalently bonded to another metal fragment or an alkyl group; examples are the complexes [LnM-M'(CO)3(a-diimine)] (LnM = (CO)5Mn , (CO)5Re , (CO)4C0, Ph3Sn ' etc. ; M' = Mn, Re) [1][2][3][4][5][6][7][8], [Re(R)(CO)3(a-diimine)] [9], [RuI(ipr)(CO)2(iPr-DAB)] [10] and [Zn(R)2(R'-DAB) ] [11]. With exception of the Zn compounds, all these complexes are characterized by strongly allowed metalto-o~-diimine (MLCT) transitions in the visible region.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]

Nieuwenhuis

Loon

Moraal

et al. 1995

Journal of Organometallic Chemistry

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Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. The photochemical quantum yield for the disappearance of the ipr-DAB complex was ca. 0.30, but only 0.05 for the iPr-PyCa complex. Low-temperature measurements and flash photolysis data showed that this difference in behaviour is due to the thermal instability of the dimer [Ru(Me)(CO)2(ipr-PyCa)]2, which leads to partial regeneration of the parent complex at room temperature. At temperatures below 163 K, the photodecomposition into radicals was followed by electron transfer, leading to formation of the ions [(CO)sMn]-and [Ru(Me)(SXCO)z(a-diimine)] + in 2-MeTHF and the contact ion-pair [(CO)sMn-... Ru(Me)(CO)z(a-diimine) +] in 2-chlorobutane. Similar photodisproportionation products were formed upon irradiation of thc complexes at room temperature in the presence of N-or P-donor ligands.

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Photo-initiated polymerization of cyclohexene oxide by dirhenium decacarbonyl

Abu-Abdoun

1999

Polym. Int.

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Photochemistry of metal—metal bonded complexes

Cited by 43 publications

References 24 publications

Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with α-diimine ligands. X-ray structure of [(CO)5MnRu(Me)(CO)2(σ(N′)-iPr-PyCa)] (iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine)

Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with α-diimine ligands. X-ray structure of [(CO)5MnRu(Me)(CO)2(σ(N′)-iPr-PyCa)] (iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine)

Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]

Photo-initiated polymerization of cyclohexene oxide by dirhenium decacarbonyl

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