Linear vs. bent nitrosyl ligands in pseudotetrahedral nitrosyl complexes. Low-temperature structure of CoI(NO)2(P(C6H5)3)

Haymore, Barry L.; Huffman, John C.; Butler, Nancy E.

doi:10.1021/ic00143a036

Cited by 24 publications

(6 citation statements)

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“…The appearance of these NO stretching bands indicates the formation of dinitrosyl complexes, examples of which display symmetric and asymmetric stretching modes between 1750-1798 and 1820-1876 cm -1 . [53][54][55][56][57][58][59][60] In addition to the similarity of our ν NO bands to those in these examples, they are suggestive of those at 1809 and 1730 cm -1 for the nondansylated parent complex, [Co(NO) 2 (i-Pr 2 ATI)] (21). The shift to higher energy in the spectra of 20a-c is expected owing to the electron-withdrawing sulfonamides of the DATI ligands.…”

Section: Resultssupporting

confidence: 73%

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Aminotroponiminates as Ligands for Potential Metal-Based Nitric Oxide Sensors

et al. 2000

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A family of new fluorescently labeled ligands, HRDATI, was prepared to develop transition-metal-based NO sensing strategies. The ligands are composed of aminotroponiminates (ATIs) with a dansyl fluorophore on one of the imine nitrogen atoms and an alkyl substituent, either i-Pr (8), t-Bu (9), or Bz (10), on the other. Bis(chelate) Co2+ ([Co(i-PrDATI)2] (12), [Co(t-BuDATI)2] (14), [Co(BzDATI)2] (15)) and Zn2+ ([Zn(i-PrDATI)2] (13)) complexes were prepared and characterized by X-ray crystallography. The bis(ATI) complex [Co(i-Pr2ATI)2] (11) was also prepared and its X-ray crystal structure determined. Cyclic voltammetry reveals reversible redox waves at -2.57 and -0.045 V (vs Cp2Fe/Cp2Fe+) in THF for the Co2+/Co+ and Co3+/Co2+ couples, respectively, of 11. Only a Co2+/Co+ wave at -2.09 V is observed for 12. When excited at 350 nm, the HRDATI ligands and the diamagnetic Zn2+ complex 13 fluoresce around 500 nm, whereas the paramagnetic Co2+ complexes quench the fluorescence. These air-stable cobalt compounds react with nitric oxide to dissociate a DATI ligand and form neutral dinitrosyl complexes, [Co(NO)2(RDATI)]. The release of the fluorophore-containing ligand is accompanied by an increase in fluorescence intensity, thus providing a strategy for fluorescent NO sensing. Linking two DATI moieties via a tetramethylene chain affords the ligand H2DATI-4 (18). The Co2+ complex [Co(DATI-4)] (19) reacts more readily with NO than the bis(DATI) compounds and also displays an increase in fluorescence intensity upon NO binding.

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Section: Resultssupporting

confidence: 73%

“…For 20b and 20c , the corresponding values are 1833, 1760 cm -1 and 1833, 1755 cm -1 , respectively. The appearance of these NO stretching bands indicates the formation of dinitrosyl complexes, examples of which display symmetric and asymmetric stretching modes between 1750−1798 and 1820−1876 cm -1 . − …”

Section: Resultsmentioning

confidence: 99%

Aminotroponiminates as Ligands for Potential Metal-Based Nitric Oxide Sensors

et al. 2000

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“…The IR bands indicate formation of a Co ± dinitrosyl species and are at the low end of the range for tetrahedral {Co(NO) 2 } 10 complexes, which exhibit symmetric and asymmetric NO stretching bands between 1820 ± 1876 cm À1 and between 1755 ± 1798 cm À1 . [18] In some cases, formation of {Co(NO) 2 } 10 species proceeds by disproportionation of Co II L 2 in the presence of NO to afford [Co I (NO) 2 L] and [Co III L 3 ], where L is a bidentate ligand. [19,20] There is no apparent evidence for a Co III species in the reaction of 2 with NO and, at present, the nature of the reductant is unknown.…”

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confidence: 99%

Metal-Based NO Sensing by Selective Ligand Dissociation

Franz

Singh

Lippard

2000

Angew. Chem. Int. Ed.

107

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“…1979 Selected bond lengths (A) and angles (deg): Co-Cl 2.262 (2), Co-P 2.244 (2), Co-N, 1.662 (6), Co-N2 1.662 (7), NrO! 1.142 (8), N2-Q2 1.142 (9), Co-.-Nj 3.682 (6), ••• 3 2.978 (7), Cl---N3 3.522 (5), Cl-Co-P 97.39 (7), Cl-Co-Nj 113.4 (3), Cl-Co-N2 115.8 (3), P-Co-N, 99.7 (2), P-Co-N2108.8 (2), N,-Co-N2118.0 (3), Co-,-, 162.7 (7),…”

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confidence: 99%