Heteroleptic arene ruthenium complexes based on meso-substituted dipyrrins: synthesis, structure, reactivity, and electrochemical studies.
First examples of heteroleptic arene ruthenium complexes containing dipyrrin ligands with the general formulations [(eta(6)-arene)RuCl(L)] [(arene = C(6)H(6), C(10)H(14); L = 5-(4-cyanophenyl)-dipyrromethene, cydpm; 5-(4-nitrophenyl)-dipyrromethene, ndpm and 5-(4-benzyloxyphenyl)-dipyrromethene, bdpm] have been synthesized. The complexes [(eta(6)-C(10)H(14))RuCl(L)] (L = ndpm and cydpm) reacted with NaN(3) and NH(4)SCN to afford neutral mononuclear complexes [(eta(6)-C(10)H(14))Ru(N(3))(L)] and [(eta(6)-C(10)H(14))Ru(SCN)(L)]. Their reactions with EPh(3) (E = P, As) and exobidentate ditopic P-P and N-N donor ligands, namely, bis-(diphenylphosphino)methane (dppm) and 4,4'-bipyridine (bpy) in the presence of AgSO(3)CF(3) afforded cationic mono- and binuclear complexes [(eta(6)-C(10)H(14))Ru(L)(EPh(3))]SO(3)CF(3), [{(eta(6)-C(10)H(14))Ru(L)}(2)(mu-dppm)](SO(3)CF(3))(2), and [{(eta(6)-C(10)H(14))Ru(L)}(2)(mu-bpy)](SO(3)CF(3))(2), respectively. The reaction products have been characterized by analytical and spectral studies. Molecular structures of the representative complexes [(eta(6)-C(10)H(14))RuCl(cydpm)], [(eta(6)-C(6)H(6))RuCl(cydpm)], [(eta(6)-C(10)H(14))RuCl(ndpm)], [(eta(6)-C(10)H(14))Ru(N(3))(ndpm)], and [(eta(6)-C(10)H(14))Ru(PPh(3))(ndpm)]SO(3)CF(3) have been determined crystallographically. Redox behavior of the complexes has been investigated by electrochemical studies. Emission spectral studies at room temperature suggested that the complexes under study are non-emissive.
Yadav
Mahendra
M
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi - 221 005 (U.P.), India.
Singh
Ashish Kumar
AK
Maiti
Biswajit
B
Pandey
Daya Shankar
DS
D018360:Crystallography, X-Ray; D004563:Electrochemistry; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D015203:Reproducibility of Results; D012428:Ruthenium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D006841:Hydrocarbons, Aromatic; D008024:Ligands; D009942:Organometallic Compounds; D012428:Ruthenium