1992
DOI: 10.1021/ic00041a020
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Novel and stable metal-metal-bonded diruthenium(I) complexes containing TCNX0/.bul.- in both the inner and the outer coordination sphere (TCNX = TCNE, TCNQ). A combined EPR/ENDOR-, UV/visible/near-IR-, and IR-spectroscopic and electrochemical investigation

Abstract: Reaction of the diphosphazane-bridged diruthenium derivatives Ru2(M-CO)(CO)4[u-(RO)2PN(Et)P(OR)2]2 (R = Me, 'Pr) with the electron acceptors TCNX (X = Q, E) affords products of the type {Ru2(CO)5[/it-(R0)2PN-(Et)P(OR)2]2(s1-TCNX)}(TCNX) containing a TCNX radical anion in both the inner and outer coordination sphere of the cation. The contribution of the coordinated TCNX*™ to the EPR/ENDOR and UV/vis/near-IR spectra of these salts is partly obscured by that of the external, completely dissociated ¿^/.-symmetric… Show more

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Cited by 52 publications
(21 citation statements)
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“…The peak to peak linewidth, ∆H pp , is 0.06 mT for g ⊥ and the width at half height, ∆H 1/2 , is 0.09 mT for g || . This result compares well to the literature g-values for the radical anions of ~2.002 for similar acceptors like TCNQ and TCNE [25]. In contrast, TMPD:TCNQ forms a π-π complex with a diamagnetic ground state.…”
Section: Resultssupporting
confidence: 89%
“…The peak to peak linewidth, ∆H pp , is 0.06 mT for g ⊥ and the width at half height, ∆H 1/2 , is 0.09 mT for g || . This result compares well to the literature g-values for the radical anions of ~2.002 for similar acceptors like TCNQ and TCNE [25]. In contrast, TMPD:TCNQ forms a π-π complex with a diamagnetic ground state.…”
Section: Resultssupporting
confidence: 89%
“…Figure 1A also shows absorption spectra of reduced TCNQ produced by bulk electrolysis in the presence of TBAPF 6 ("TBA + /TCNQ 1-", red), as described in the Experimental Methods section, and of a dispersion of PbS QDs with 2.5 added equivalents of TCNQ (black) after subtraction of the spectrum of QDs alone. The shape of the spectrum of TCNQ in the presence of QDs is very similar to the spectrum of electrochemically reduced TCNQ, which contains characteristic TCNQ 1-absorption features at 686, 749 and 850 nm; [1,12,13] these spectra indicate that spontaneous electron transfer from PbS QDs to TCNQ forms a stable QD 1+ /TCNQ 1-complex. From the intensity of the signal corresponding to neutral TCNQ (centered at 400 nm, not shown), we calculate that the mixture of QDs with TCNQ contains 2.4 µM of neutral TCNQ in solution, and therefore (4.2 -2.4 =) 1.8 µM of reduced TCNQ in the sample (there is no signal from TCNQ 2-).…”
Section: Resultsmentioning
confidence: 60%
“…Using the observed absorbance of reduced TCNQ at 842 nm (0.026 a.u), we calculate the extinction coefficient of the surface-adsorbed, reduced TCNQ to be 14,000 cm -1 M -1 , which is a factor of 3 smaller than the published value of 43,300 cm -1 M -1 in CH 2 Cl 2 . [12] For comparison, we have scaled the spectrum of pre-electrolyzed TCNQ 1-such that the two spectra correspond to the same concentrations of reduced TCNQ; we see, again, that the signal from free TCNQ 1-in solution is a factor of 3 larger than that of the TCNQ reduced in situ.…”
Section: Resultsmentioning
confidence: 89%
“…Changes in the IR spectrum of 1 on stepwise reduction to the monoanion (top) and from the monoanion to the dianion (bottom) from spectroelectrochemistry in CH 2 Cl 2 /0.1 M Bu 4 NPF 6 . contrast, the oxidized 2 ' showed an unresolved signal at 2.0030, compatible with a complex of TCNQ +( [20].…”
Section: Nmr and Epr Spectroscopymentioning
confidence: 98%