Alkyl-dependent photochemistry of Mn (R)(CO)3(R′-DAB) (R = Me, Bz; R′ = iPr, pTol): homolysis of the MnR bond for R = Bz and release of CO for R = Me

Rossenaar, Brenda D.; Stufkens, Derk J.; Oskam, A.; Fraanje, Jan; Goubitz, K.

doi:10.1016/0020-1693(95)04962-2

Cited by 53 publications

(33 citation statements)

References 53 publications

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“…The photolysis led to a progressive depletion of the vco bands at 2044 and 1954 cm-' concomitantly with the appearance of new bands at 1872 and 1991 cm-'. This new band profile is similar to that exhibited byfuc-[Mn(Me)(C0)3(RDAB)], where DAB is 1,4-diaza-1,3-butadiene, vCo = 1990, 1900(br) cm-' and I,,, = 340,502 nm(30). Free CO was not detected during the photoreaction.…”

supporting

confidence: 77%

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)₃(phen)(lmidazole)](SO₃CF₃) Complexes^¶

Carlos

Neto

Neumann

2004

Photochem & Photobiology

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Photochemical and photophysical data are reported for a series of fac‐[Mn(CO)3(phen)(Im‐R)](SO3CF3) complexes, where phen is 1,10‐phenanthroline and Im is imidazole. Intraligand and metal‐to‐ligand charge transfer (MLCT) transitions are observed in the electronic absorption spectra of these complexes and are sensitive to the nature of the ligand substituent. At room temperature the emission spectra show a clear progression from broad structureless MLCT to highly structured π‐π* emission on going from R = ‐H, ‐CH3, ‐C6H5, to ‐Metro, where Metro is 2‐methyl‐5‐nitroimidazole. Even at low temperatures the latter complexes show only the π‐π* emission. The trend in the photophysical properties found in the emission spectra parallels the changes in the photochemical properties with the electron‐donating or electron‐withdrawing power of the substituent on the imidazole ligand. Although MLCT irradiation of the complexes with R = ‐H, ‐CH3 leads to the mer‐[Mn(CO)3(phen)(Im‐R)]+ isomers, the complexes with the imidazole ligand substituted by ‐C6H5 or ‐Metro release the Im‐R ligand and produce the stereoretentive fac‐[Mn(CO)3(phen)(S)]+ complexes. The stereochemical fate and mechanistic implications of the photolysis reactions are discussed in terms of the nature of ligand substitution.

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supporting

confidence: 77%

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)₃(phen)(lmidazole)](SO₃CF₃) Complexes^¶

Carlos

Neto

Neumann

2004

Photochem & Photobiology

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“…This later reaction may certainly compete with the emission process either from the 1 MLCT absorbing state or from the low-lying 3 MLCT states, according to the schematic view of the potential energy curves (Scheme 1). This is corroborated by the experimental quantum yield of the Re-L bond homolysis which may vary between 10 -2 (L = methyl) to nearly 1.0 (L = ethyl or benzyl) [6,7] in these molecules.…”

Section: Introductionsupporting

confidence: 60%

Emission spectroscopy of metal-to-ligand-charge-transfer states of HRe(CO)3(H-dab), model system for α-diimine rhenium tricarbonyl complexes

Villaume

Daniel

2005

Comptes Rendus. Chimie

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“…[63][64][65][66][67][68][69][70][71][72][73][74] The mechanism of photodecomposition for [MnX(N-N)(CO) 3 ]-type compounds has been suggested to involve equatorial CO loss following the population of a dissociative ligand-field state after MLCT. [63][64][65][66][67][68][69][70][71][72][73][74] The mechanism of photodecomposition for [MnX(N-N)(CO) 3 ]-type compounds has been suggested to involve equatorial CO loss following the population of a dissociative ligand-field state after MLCT.…”

Section: Photodecompositionmentioning

confidence: 99%

“…The sensitivity of Mn(I)-tricarbonyl complexes to UV-vis light has been widely reported. [63][64][65][66][67][68][69][70][71][72][73][74] The mechanism of photodecomposition for [MnX(N-N)(CO) 3 ]-type compounds has been suggested to involve equatorial CO loss following the population of a dissociative ligand-field state after MLCT. Subsequently, the axial halogen rearranges to fill the vacant equatorial position and the resulting axial void is filled with a solvent molecule (see Scheme 1 in ref.…”

Section: Photodecompositionmentioning

confidence: 99%

Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)₃] complexes

et al. 2015

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The synthesis, electrochemical activity, and relative photodecomposition rate is reported for four new Mn(i) N-heterocyclic carbene complexes: [MnX(N-ethyl-N'-2-pyridylimidazol-2-ylidine)(CO)3] (X = Br, NCS, CN) and [MnCN(N-ethyl-N'-2-pyridylbenzimidazol-2-ylidine)(CO)3]. All compounds display an electrocatalytic current enhancement under CO2 at the potential of the first reduction, which ranges from -1.53 V to -1.96 V versus the saturated calomel electrode. Catalytic CO production is observed for all species during four-hour preparative-scale electrolysis, but substantial H2 is detected in compounds where X is not Br. All species eventually decompose under both 350 nm and 420 nm light, but cyanide substituted complexes (X = CN) last significantly longer (up to 5×) under 420 nm light as a result of a blue-shifted MLCT band.

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Alkyl-dependent photochemistry of Mn (R)(CO)3(R′-DAB) (R = Me, Bz; R′ = iPr, pTol): homolysis of the MnR bond for R = Bz and release of CO for R = Me

Cited by 53 publications

References 53 publications

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)₃(phen)(lmidazole)](SO₃CF₃) Complexes^¶

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)₃(phen)(lmidazole)](SO₃CF₃) Complexes^¶

Emission spectroscopy of metal-to-ligand-charge-transfer states of HRe(CO)3(H-dab), model system for α-diimine rhenium tricarbonyl complexes

Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)₃] complexes

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Alkyl-dependent photochemistry of Mn (R)(CO)3(R′-DAB) (R = Me, Bz; R′ = iPr, pTol): homolysis of the MnR bond for R = Bz and release of CO for R = Me

Cited by 53 publications

References 53 publications

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)3(phen)(lmidazole)](SO3CF3) Complexes¶

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)3(phen)(lmidazole)](SO3CF3) Complexes¶

Emission spectroscopy of metal-to-ligand-charge-transfer states of HRe(CO)3(H-dab), model system for α-diimine rhenium tricarbonyl complexes

Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)3] complexes

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The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)₃(phen)(lmidazole)](SO₃CF₃) Complexes^¶

The Effects of the Substitution on the lmidazole Ligand on the Photochemical Properties of fac[Mn(CO)₃(phen)(lmidazole)](SO₃CF₃) Complexes^¶

Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)₃] complexes