Electrochemical oxidation of isocyanide complexes of manganese and chromium

Treichel, P. M.; Dirreen, Glen E.

doi:10.1016/s0022-328x(00)88893-2

Cited by 25 publications

(11 citation statements)

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“…Iron(II) is by far most investigated in this regard, 28 − 44 yet only a handful of iron(II) complexes with MLCT lifetimes in the nanosecond time regime are known. 28 , 29 , 41 Building on early reports of hexakis(arylisocyanide) manganese(I) complexes with a focus on UV–vis absorption and electrochemical properties, 45 − 52 we recently discovered that manganese(I) complexes with chelating bi- and tridentate ligands have luminescent and photoredox active MLCT states. 53 Until now, the synthesis of these chelates has remained laborious, 54 and therefore it seemed attractive to explore the possibility of using more directly accessible monodentate arylisocyanides for manganese(I) complexes with luminescent MLCT states.…”

Section: Introductionmentioning

confidence: 99%

Manganese(I) Complex with Monodentate Arylisocyanide Ligands Shows Photodissociation Instead of Luminescence

et al. 2022

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Recently reported manganese(I) complexes with chelating arylisocyanide ligands exhibit luminescent metal-to-ligand charge-transfer (MLCT) excited states, similar to ruthenium(II) polypyridine complexes with the same d 6 valence electron configuration used for many different applications in photophysics and photochemistry. However, chelating arylisocyanide ligands require substantial synthetic effort, and therefore it seemed attractive to explore the possibility of using more readily accessible monodentate arylisocyanides instead. Here, we synthesized the new Mn(I) complex [Mn(CNdippPh OMe2 ) 6 ]PF 6 with the known ligand CNdippPh OMe2 = 4-(3,5-dimethoxyphenyl)-2,6-diisopropylphenylisocyanide. This complex was investigated by NMR spectroscopy, single-crystal structure analysis, high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) measurements, IR spectroscopy supported by density functional theory (DFT) calculations, cyclic voltammetry, and time-resolved as well as steady-state UV–vis absorption spectroscopy. The key finding is that the new Mn(I) complex is nonluminescent and instead undergoes arylisocyanide ligand loss during continuous visible laser irradiation into ligand-centered and charge-transfer absorption bands, presumably owed to the population of dissociative d–d excited states. Thus, it seems that chelating bi- or tridentate binding motifs are essential for obtaining emissive MLCT excited states in manganese(I) arylisocyanides. Our work contributes to understanding the basic properties of photoactive first-row transition metal complexes and could help advance the search for alternatives to precious metal-based luminophores, photocatalysts, and sensors.

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Section: Introductionmentioning

confidence: 99%

Manganese(I) Complex with Monodentate Arylisocyanide Ligands Shows Photodissociation Instead of Luminescence

et al. 2022

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“…complexes preceded the synthetic studies cited above. 3,4 Both suggest that simple electron-transfer reactions should be easily accomplished with mild oxidizing agents, and both predict the stable existence of the resulting oxidized species. One observation made in earlier work on the Cr(CNR)6 complexes was that substituent groups on the aryl ring of the isocyanide have some influence on the Ex¡2 value.…”

Section: Introductionmentioning

confidence: 99%

“…Data on the [Mn(CNR)6]+ -* [Mn(CNR)6]2+ + e' oxidations show the same trends; here the existence of complexes of alkyl isocyanides allows their inclusion and comparison. 3,5 The ease of oxidation of both the chromium and manganese complexes is related to the donor ability of the ligand groups, their ability to cause a buildup of negative charge on the metal. Manganese complexes of alkyl isocyanides have lower Ex¡2 values than comparable complexes of aryl isocyanides.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry of a series of hexakis(aryl isocyanide)chromium(0) complexes

Essenmacher¹,

Treichel²

1977

Inorg. Chem.

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“…(1) For part 9 of this series see: R. B. (2) Portions of this work were presented at the 28th Southeast Regional Chem., IS, 879 (1976).…”

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Electrochemical studies on [Mn(CNR)6]+ complexes

Treichel¹,

Mueh²

1977

Inorg. Chem.

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Electrochemical Studies on [Mn(CNR),]+ Complexes derivative with Mn CO 5X X = Br or Cl) gave only with C5H5Mo(N0)2Cl in diethyl ether gave an unidentified yellow solid suggested by its NMR spectrum to contain (CH3),Sn groups but neither C5H5 nor (CH3)2C groups. Reaction of (CH3)2C=NOSn(CH3)3 with C5H5Fe(CO)2C1 in boiling benzene gave only (CH3)3SnFe(C0)2C5H5.'' No tractable products were obtained from reactions of (CH3)2-in ethereal solvents at or near room temperature. These observations suggest that the range of transition metal systems to which (CH3)2C=NOSn(CH3)3 can transfer (CH3)2CN0 groups is extremely limited and that in some cases this tin reagent instead transfers (CH3)$n or possibly (CH3),Sn0 units to the transition metal system. Acknowledgment. We are indebted to the National Science Foundation for partial support of this work under Grant CHE-75-19974. We are also indebted to M and T Chemical Co. for generous gifts of trimethyltin chloride. Registry No. MezCNOMo(CO)zCp, 61491-36-9; (CH2)&!NOMo(C0)2Cp, 61 81 3-21-6; (CHz=CH)(Me)CNOMo-(CO)zCp, 618 13-22-7; (MezC=CH)(Me)CNOMo(CO)zCp, 61813-23-8;CHz=CH(CH2)zC(Me)NOMo(CO)2Cp, 61813-24-9; (CH3)3SnMn(CO)5.' 0 ' Reaction of (CH3)2C=NOSn(CH3)3 Me2CNOW(C0)zCp, 6 18 13-25-0; (CH2)5CNOW(C0)2Cp, 618 13-26-1; (CHz=CH)(Me)CN0W(CO),Cp, 618 13-27-2; (MezC=CH)(Me)CNOW(CO)2Cp, 61 81 3-28-3; CH2=CH-(CHz)zC(Me)NOW(CO)zCp, 61813-29-4; (CH3)zC==NOSn(CH3)3, 25092-7 1-1; (CH3)zC=CHC(CH3)=NOSn(CH3)3, 61 8 12-49-5; HzC=CH(CH2)zC(CH3)=NOSn(CH3)3, 61812-50-8; CSHS-

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Electrochemical oxidation of isocyanide complexes of manganese and chromium

Cited by 25 publications

References 1 publication

Manganese(I) Complex with Monodentate Arylisocyanide Ligands Shows Photodissociation Instead of Luminescence

Manganese(I) Complex with Monodentate Arylisocyanide Ligands Shows Photodissociation Instead of Luminescence

Electrochemistry of a series of hexakis(aryl isocyanide)chromium(0) complexes

Electrochemical studies on [Mn(CNR)6]+ complexes

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