De, Prinaka ; Mondal, Tapan Kumar ; Mobin, Shaikh M. ; Lahiri, Goutam Kumar (2011) Electronic structures and reactivity aspects of ruthenium-nitrosyls Inorganica Chimica Acta, 372 (1). pp. 250-258. ISSN 0020-1693
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Official URL: http://www.sciencedirect.com/science/article/pii/S...
Related URL: http://dx.doi.org/10.1016/j.ica.2011.01.077
Abstract
Nitrosyl complexes with {Ru-NO}6 (4(ClO4)3) and {Ru-NO}7 (4(ClO4)2) configurations have been isolated in the selective molecular framework of [Ru(tpm)(pap)(NO)]n+ (tpm = tris(1-pyrazolyl)methane and pap = 2-phenylazopyridine). The DFT optimized structures of [RuII(tpm)(pap)(NO+)]3+ (43+) and [RuII(tpm)(pap)(NO)]2+ (42+) predict that the Ru-N-O groups in the complexes are in almost linear and bent geometries, respectively. In agreement with largely NO centered reduction a sizeable shift in ν(NO) frequency of 324 cm-1 has been observed on moving from {RuII-NO+} state in 43+ to {RuII-NO) state in 42+. The DFT proposed NO centered spin in {RuII-NO) (42+) (Mulliken spin-densities: 0.860 (NO) and 0.087 (Ru)) has been evidenced by its free radical EPR spectrum with g = 1.989. The strongly electrophilic {RuII-NO+} state in 43+ (ν(NO): 1962 cm-1) can be transformed to the corresponding {RuII - NO2 -}complex (3+) in the presence of nucleophile, OH- with k = 2.03 × 10-1 M-1 s-1 at 298 κ in CH3CN. On irradiation with light the acetonitrile solution of [RuII(tpm)(pap)(NO+)]3+ (43+) undergoes facile photorelease of NO (kNO, s-1 = 0.1 × 10-1 and t½ , s = 69.3) with the concomitant formation of the solvate [RuII(tpm)(pap)(CH3CN)]2+ (22+). The photoreleased NO can be trapped as an Mb-NO adduct.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to Elsevier Science. |
| Keywords: | Ruthenium; Nitrosyl; Electrochemistry; Spectra; DFT; Photocleavage |
| ID Code: | 88364 |
| Deposited On: | 29 Mar 2012 04:47 |
| Last Modified: | 29 Mar 2012 04:47 |
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