212009-62-6Relevant academic research and scientific papers
Preparations and structures of (η6-arene)ruthenium(II) complexes bearing 1,1′-bis(diphenylphosphinomethyl)ferrocene or 1,1′-bis(diphenylphosphino)ferrocene
Mai, Jian-Fang,Yamamoto, Yasuhiro
, p. 223 - 232 (1998)
Reactions of bis[dichloro(η6-arene)ruthenium] 1 with 1,1′-bis[(diphenylphosphino)methyl]ferrocene (dpmf) gave the dpmf-P,P′ bridged complexes [(η6-arene)RuCl2]2(μ-dpmf) 2, where arenes=(a) 1,2,3,4-Me4C6H2; (b) C6Me6; (c) p-cymene; (d) 1,2,3,5-Me4C6H2; (e) 1,3,5-Me3C6H3; (f) 1,2,3-Me3C6H3. Treatment of 2 with xylyl isocyanide (XylNC) in the presence of NaPF6 produced the F-coordinated complex [(η6-arene)RuCl]2(μ-dpmf)(PF6)2 3a without containing XylNC. Reactions of 1 with 1,1′-bis(diphenylphosphino)ferrocene (dppf) formed the bridged complexes [(arene)RuCl2]2(μ-dppf)] 4, as well as the dpmf complexes. The similar reactions in the presence of NaPF6 gave the chelated complexes [(η6-arene)RuCl(dppf-P,P′)](PF6) 5. Crystal structures of 2a, 2d·2CH2Cl2, 4a·CH2Cl2 and 5b were confirmed by X-ray analyses and they have three-legged piano-stool structures. Crystal data are as follows: 2a triclinic, space group P1, with a=12.802(6), b=19.111(6), c=11.438(4) A, α=98.93(3), β=108.57(3), γ=90.42(3)°, V=2615(1) A3, Z=2 [R=0.051, Rw=0.052 for 4114 independent reflections with I>3.0σ(I)]; 2d·2CH2Cl2 monoclinic, space group C2/c, a=38.379(6), b=9.903(3), c=17.381(4) A, β=113.91(1)°, V=6038 A3 and Z=4 [R=0.057, Rw=0.054 for 1882 independent reflections with I>3.0σ(I)]; 4a·CH2Cl2 triclinic P1, with a=15.044(7), b=17.664(3), c=10.586(2) A, α=99.64(2), β=95.85(2), γ=94.74(2)°, V=2744(1) A3, Z=2 [R=0.065, Rw=0.072 for 4301 independent reflections I>3.0σ(I)]; 5b monoclinic, space group P21/n, a=15.036(4), b=17.192(5), c=15.983(3) A, β=92.92(2)°, V=4126(1) A3, Z=4 [R=0.070, Rw=0.079 for 3389 independent reflections I>3σ(I)]. Conformation of the ferrocenyl skeletons were determined by dihedral angles containing two Cp rings. In cyclic voltammertry (CV) of these complexes the Fe(II)/Fe(III) redox couples were quasi-reversible, but the Ru moieties were irreversible.
