Preparations and structures of ( η6-arene)ruthenium(II) complexes bearing 1,1′-bis(diphenylphosphinomethyl)ferrocene or 1,1′-bis(diphenylphosphino)ferrocene

Abstract

Reactions of bis[dichloro( η 6-arene)ruthenium] 1 with 1,1′-bis[(diphenylphosphino)methyl]ferrocene (dpmf) gave the dpmf- P,P′ bridged complexes [( η 6-arene)RuCl 2] 2( μ-dpmf) 2, where arenes=( a) 1,2,3,4-Me 4C 6H 2; ( b) C 6Me 6; ( c) p-cymene; ( d) 1,2,3,5-Me 4C 6H 2; ( e) 1,3,5-Me 3C 6H 3; ( f) 1,2,3-Me 3C 6H 3. Treatment of 2 with xylyl isocyanide (XylNC) in the presence of NaPF 6 produced the F-coordinated complex [( η 6-arene)RuCl] 2( μ-dpmf)(PF 6) 2 3a without containing XylNC. Reactions of 1 with 1,1′-bis(diphenylphosphino)ferrocene (dppf) formed the bridged complexes [(arene)RuCl 2] 2( μ-dppf)] 4, as well as the dpmf complexes. The similar reactions in the presence of NaPF 6 gave the chelated complexes [( η 6-arene)RuCl(dppf- P,P′)](PF 6) 5. Crystal structures of 2a, 2d·2CH 2Cl 2, 4a·CH 2Cl 2 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 P 1 , with a=12.802(6), b=19.111(6), c=11.438(4) Å, α=98.93(3), β=108.57(3), γ=90.42(3)°, V=2615(1) Å 3, Z=2 [ R=0.051, R w =0.052 for 4114 independent reflections with I>3.0 σ(I)]; 2d·2CH 2Cl 2 monoclinic, space group C2/ c, a=38.379(6), b=9.903(3), c=17.381(4) Å, β=113.91(1)°, V=6038 Å 3 and Z=4 [ R=0.057, R w =0.054 for 1882 independent reflections with I>3.0 σ( I)]; 4a·CH 2Cl 2 triclinic P 1 , with a=15.044(7), b=17.664(3), c=10.586(2) Å, α=99.64(2), β=95.85(2), γ=94.74(2)°, V=2744(1) Å 3, Z=2 [ R=0.065, R w =0.072 for 4301 independent reflections I>3.0 σ( I)]; 5b monoclinic, space group P2 1/ n, a=15.036(4), b=17.192(5), c=15.983(3) Å, β=92.92(2)°, V=4126(1) Å 3, Z=4 [ R=0.070, R w =0.079 for 3389 independent reflections I>3 σ( 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.