Primary and Secondary Phosphane Complexes of Metalloporphyrins: Isolation, Spectroscopy, and X‐ray Crystal Structures of Ruthenium and Osmium Porphyrins Binding Phenyl‐ or Diphenylphosphane

Xie, Jin; Huang, Jie‐Sheng; Zhu, Nianyong; Zhou, Zhóngyuan; Che, Chi‐Ming

doi:10.1002/chem.200400996

Cited by 22 publications

(14 citation statements)

References 110 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The same procedure has been successfully applied to the preparation of pentahydride-diphenylphosphine Os(IV) complexes and the detected intermediates support the proposed mechanism 119. Although other less common oxidation states have been explored in osmium-SPO complexes, such as the porphyrin-Os(VI) derivatives described by Che and coworkers,120 an increasing interest have appeared in the design of bidentate and…”

mentioning

confidence: 68%

Coordination chemistry and catalysis with secondary phosphine oxides

Gallen

Riéra

Verdaguer

et al. 2019

Catal. Sci. Technol.

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 68%

Coordination chemistry and catalysis with secondary phosphine oxides

Gallen

Riéra

Verdaguer

et al. 2019

Catal. Sci. Technol.

View full text Add to dashboard Cite

show abstract

“…The PPh 2 Me ligands in both complexes adopt a trans-configuration, with Os-P distances in the range of 2.325-2.352 Å, which are comparable to that of the red-emitting Os(II) complex [Os(fppz) 2 (PPh 2 Me) 2 ] (2.362 Å) 19 and the corresponding porphinato (2.369 Å) and the benzotriazolato analogues (2.353 Å). 20,21 Moreover, it is notable that the pyridyl group in 3 is located trans to the strong σ-donating hydride ligand. This unique feature has caused a lengthening of the Os-N(py) distance in 3 (Os-N(1) ) 2.190 Å), compared with that of its geometric isomer 4 (Os-N(1) ) 2.166 Å), for which the pyridyl unit is located trans to the π-accepting CO ligand.…”

Section: Resultsmentioning

confidence: 99%

En Route to the Formation of High-Efficiency, Osmium(II)-Based Phosphorescent Materials

Hsu¹,

Tung²,

Chi³

et al. 2006

Inorg. Chem.

View full text Add to dashboard Cite

Triosmium cluster complexes [Os3(CO)8(fppz)2] (2a) and [Os3(CO)8(fptz)2] (2b) bearing two 2-pyridyl azolate ligands were synthesized in an attempt to establish the reaction mechanism that gives rise to the blue-emitting phosphorescent complexes [Os(CO)2(fppz)2] (1a) and [Os(CO)2(fptz)2] (1b) [(fppz)H = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole; (fptz)H = 3-(trifluoromethyl)-5-(2-pyridyl)triazole]. X-ray structural analysis of 2b showed an open triangular metal framework incorporating multisite-coordinated 2-pyridyltriazolate ligands. Treatment of 2 with the respective 2-pyridylazolate ligand led to the formation of blue-emitting complex 1b, confirming their intermediacy, while the reaction of 2b with phosphine ligand PPh2Me afforded two hitherto novel hydride complexes 3 and 4, for which the reversible interconversion was clearly established at higher temperatures (> 180 degrees C). The single-crystal X-ray diffraction analyses of 3 and 4 confirmed their monometallic and isomeric nature, together with the coordination of two phosphine ligands located in the trans-disposition and one CO and one hydride located opposite to the pyridyl triazolate chelate. Subtle differences in photophysical properties were examined for isomers 3 and 4 on the basis of steady state absorption and emission, the relaxation dynamics, and temperature-dependent luminescent studies. The results, in combination with time-dependent density function theory (TDDFT) calculations, provide fundamental insights into the future design and preparation of highly efficient phosphorescent emitters.

show abstract

“…6 Ru(II) porphyrin and phthalocyanine complexes with primary and secondary phosphines were reported for phosphine functionalization and phosphinidene transfer reactions. 7,8 Likewise, Rh(III) porphyrins have been studied in metallo radical chemistry 9 and in olefin hydrofunctionalisation, 10 although these complexes are far less commonly studied. More exotic ligands such as charged phosphoranido ligands on Rh(III) porphyrins have also been reported.…”

Section: Introductionmentioning

confidence: 99%