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• W1982528627 abstract "We report the synthesis, spectroscopy, structure, and reactivity of the first examples of bis -azapentadienyl–ruthenium complexes. The parent compound, [(1,2,3-η 3 )-(5- tert -butylazapentadienyl)] 2 Ru(PPh 3 ) 2 ( 1 ), is produced by reacting Cl 2 Ru(PPh 3 ) 3 with two equivalents of potassium tert -butylazapentadienide. Treatment of 1 with CNCMe 3 , P(OMe) 3 , PMe 3 , or PEt 3 (L) in THF at room temperature yields single-ligand substitution products [(1,2,3-η 3 )-(5- tert -butylazapentadienyl)] 2 Ru(PPh 3 )(L) ( 2 , L = CNCMe 3 ; 3 , L = P(OMe) 3 ; 4 , L = PMe 3 ; 5 , L = PEt 3 ), and the double-ligand substitution product, [(1,2,3-η 3 )-(5- tert -butylazapentadienyl)] 2 Ru(PEt 3 ) 2 ( 6 ). Other double-ligand substitution products, [(1,2,3-η 3 )-(5- tert -butylazapentadienyl)] 2 Ru(L) 2 ( 7 , L = PMe 3 ; 8 , L = P(OMe) 3 ), are obtained when 1 is treated with PMe 3 or P(OMe) 3 in THF at reflux. Compounds 7 and 8 exist in solution as equilibrium mixtures of two structural isomers. Electron-rich compounds 6 and 7 react with triflic acid to generate dicationic products,{[(1,2,3-η 3 )-(CH 2 CHCHCH N(H)(CMe 3 )] 2 Ru(L) 2 } 2+ ( − O 3 SCF 3 ) 2 ( 9 , L = PEt 3 ; 10 , L = PMe 3 ), in which both azapentadienyl nitrogen atoms have been protonated. All of the compounds reported herein have been characterized by NMR spectroscopy, and the structures of 2 , 3 , 4 , 6 , and 9 have been confirmed by single-crystal X-ray diffraction. The first examples of bis -(η 3 -azapentadienyl)RuL 2 complexes have been synthesized, and a variety of structural motifs have been observed by NMR and X-ray diffraction. Treatment of electron-rich members of this family with triflic acid leads to protonation at both azapentadienyl nitrogen centres. • The first examples of bis -(η 3 -azapentadienyl)RuL 2 complexes have been synthesized and characterized. • The complexes adopt a variety of structural motifs, which differ in the orientation of the azapentadienyl ligands. • Dynamic interconversions between these structural types are observed. • The azapentadienyl nitrogens are the preferred sites of electrophilic attack." @default.
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• W1982528627 date "2015-04-01" @default.
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• W1982528627 title "Synthesis, spectroscopy, structure, and reactivity of bis-azapentadienyl–ruthenium–phosphine complexes [1]" @default.
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• W1982528627 doi "https://doi.org/10.1016/j.jorganchem.2015.01.006" @default.
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