Manganese(I) isocyanide complexes

Treichel, P. M.; Dirreen, Glen E.; Mueh, H.J.

doi:10.1016/s0022-328x(00)82923-x

Cited by 62 publications

(17 citation statements)

References 13 publications

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“…Shifts of the C==N stretching frequencies to higher energy by some 30-50 cm"1 on coordination are similar to those seen for manganese(I) complexes m-Mn(CO)4(CNCH3)X (X = CH2CN, Ge(C6H5)3, Sn(C6H5)3, Pb(C6H5)3, Hgl)19 and ds-Mn(CO)4-(CNCH3)Br. 20 The weak band in the 1630-1650-cm"1 region of each of the spectra is attributable to C=G rather than C=N stretching. In our compounds the presence of a single isocyanide as shown by analytical and molecular weight data as well as the observation of vc=n leaves assignment of the 1630-1650-cm"1 bands to vc=o as the only possibility.…”

Section: Resultsmentioning

confidence: 96%

Reactions of isocyanides with alkylpentacarbonylmanganese

Kuty¹,

Alexander²

1978

Inorg. Chem.

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Section: Resultsmentioning

confidence: 96%

Reactions of isocyanides with alkylpentacarbonylmanganese

Kuty¹,

Alexander²

1978

Inorg. Chem.

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“…Electron-withdrawing 2′,4′-fluorines ,, increase the redox potentials from 1 and 2 to 3 and 4 by ≤130 mV ( E red ) and ≤260 mV ( E ox ). Changing tert -butyl isocyanide ( 1 , 3 , 5 ) to the stronger π-acceptor 2,6-dimethylphenyl isocyanide ( 2 , 4 , 6 ) increases the redox potentials by ≤330 mV ( E red ) and ≤50 mV ( E ox ). Replacing a phenyl ( 1 , 2 ) with a stronger electron-donor fluorenyl ( 5 , 6 ) facilitates the oxidation by ≤310 mV.…”

Section: Resultsmentioning

confidence: 99%

Extreme Tuning of Redox and Optical Properties of Cationic Cyclometalated Iridium(III) Isocyanide Complexes

et al. 2013

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We report seven heteroleptic cationic iridium(III) complexes with cyclometalating N-arylazoles and alkyl/aryl isocyanides, [(C∧N)2Ir(CNR)2](CF3SO3), and characterize two of them by crystal structure analysis. The complexes are air- and moisture-stable white solids that have electronic transitions at very high energy with absorption onset at 320–380 nm. The complexes are difficult to reduce and oxidize; they exhibit irreversible electrochemical processes with peak potentials (against ferrocene) at −2.74 to −2.37 V (reduction) and 0.99–1.56 V (oxidation) and have a large redox gap of 3.49–4.26 V. The reduction potential of the complex is determined by the azole heterocycle (pyrazole or indazole) and by the isocyanide (tert-butyl or 2,6-dimethylphenyl) and the oxidation potential by the Ir–aryl fragment [aryl = 2′,4′-R2-phenyl (R = H/F), 9′,9′-dihexyl-2′-fluorenyl]. Three of the complexes exhibit phosphorescence in argon-saturated dichloromethane and acetonitrile solutions at room temperature with 0–0 transitions at 473–478 nm (green color; the emission spectra are solvent-independent), quantum yields of 3–25%, and long excited-state lifetimes of 62–350 μs. All of the complexes are phosphorescent at 77 K with 0–0 transitions at 387–474 nm (blue to green color). The extremely long calculated radiative lifetimes, 0.5–3.5 ms, confirm that the complexes emit from a cyclometalating-ligand-centered excited state.

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“…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%