Photochemistry of ReR(CO)3(Pri-dab)(R = Me, Et, Bn; dab = 1,4-diazabuta-1,3-diene): homolysis of the Re–R bond, its dependence on R and evidence for the reactive σbπ* state from transient absorption spectra

Rossenaar, Brenda D.; Kleverlaan, Cornelis J.; Stufkens, Derk J.; Oskam, A.

doi:10.1039/c39940000063

Cited by 38 publications

(32 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Variation of the alkyl group is expected to influence the photoreactivity of these complexes owing to a change in relative energies of the o-Tr and MLCT states. We have studied this effect and some preliminary results have been published [15].…”

Section: Ultraviolet-photoelectron Spectramentioning

confidence: 99%

“…The high photoreactivity of most of the complexes [15] caused difficulties, and it was only possible to obtain reliable EPs for the Re(Me)(CO)3(R'-DAB) complexes, using a double spinning KNO 3 pellet. Only for the least photo-active complex, Re(Me)(CO)3(pAn-DAB), an EP could be obtained in benzene using a spinning cell.…”

Section: Resonance Raman Spectroscopymentioning

confidence: 99%

“…The spectroscopic, photophysical and photochemical properties of the first set of complexes have been described elsewhere [12][13][14], while the synthesis, structural and spectroscopic properties of the second set are reported here. A preliminary account of the photochemistry of these Re complexes has appeared [15]. The general structure of the complexes is shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

Rossenaar

Kleverlaan

Ven

et al. 1995

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

Section: Ultraviolet-photoelectron Spectramentioning

confidence: 99%

Section: Resonance Raman Spectroscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

Rossenaar

Kleverlaan

Ven

et al. 1995

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

“…Studies of the complexes [Re(R)(CO)3(a-diimine)] [9] and [Rul(R)(CO)2(ipr-DAB)] [10] (R = alkyD, for which the occurrence of the homolysis reaction strongly depends on R, have shown that these reactions probably occur from a 3~rbTr * state in which one electron has been transferred from the metal-alkyl bond to the a-diimine. With exception of the [Zn(R)z(R'-DAB)] [11] complexes, such a or b ~ 17" * transition has never been observed for any of these metal-metal and metal-alkyl complexes.…”

Section: Introductionmentioning

confidence: 99%

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Bitterwolf¹

2005

Encyclopedia of Inorganic Chemistry

View full text Add to dashboard Cite

Photochemistry has evolved into a powerful tool for the highly selective generation of reactive intermediates in inorganic and organometallic chemistry. This review examines the state of the art in the examination of mechanisms of photochemical reactions utilizing techniques such as frozen matrices and fast time‐resolved methods. The application of photochemistry to the preparation of dihydrogen, alkane, and noble gas intermediates is reviewed along with the significance of these intermediates in the understanding of the mechanism of oxidative addition processes. Experiment and theory of charge transfer phenomena are extensively discussed along with the application of these processes to semiconductor and biochemical studies. Applications of photocrystallography to the examination of linkage isomers and very short‐lived excited state species are reviewed. Finally, a number of examples of the application of photochemical reactions, such as the photolysis of Fisher carbene species to generate ketenelike intermediates, to synthesis are discussed. The literature is reviewed to the end of 2003.

show abstract

Photochemistry of ReR(CO)₃(Prⁱ-dab)(R = Me, Et, Bn; dab = 1,4-diazabuta-1,3-diene): homolysis of the Re–R bond, its dependence on R and evidence for the reactive σ_bπ* state from transient absorption spectra

Cited by 38 publications

References 14 publications

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

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]

Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Contact Info

Product

Resources

About