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• 12150-46-8 1,1'-bis-(diphenylphosphino)ferrocene 

Relevant academic research and scientific papers

Synthesis, Reactivity, and Coordination of Semihomologous dppf Congeners Bearing Primary Phosphine and Primary Phosphine Oxide Groups

This contribution reports the synthesis of two phosphinoferrocene ligands desymmetrized by an inserted methylene spacer, viz., a bis-phosphine combining primary and tertiary phosphine moieties in its structure, Ph2PfcCH2PH2 (2), and a structurally unique, stable phosphine-primary phosphine oxide Ph2PfcCH2P(O)H2 (7; fc = ferrocene-1,1′-diyl). Compounds 2 and 7, together with 1,1′-bis(diphenylphosphino)ferrocene (dppf), the bis-tertiary phosphine Ph2PfcCH2PPh2, and the adduct Ph2P(BH3)fcCH2PH2 (6), were studied as ligands in Ru(II) complexes bearing auxiliary ν6-arene ligands and both free ligands and the isolated complexes were structurally authenticated, using spectroscopic methods and X-ray crystallography, and further investigated by cyclic voltammetry. The results suggest that distinct donor moieties in the unsymmetric ligands differentiate the otherwise identical coordinated metal centers and that the phosphine moiety in phosphine-phosphine oxide ligand 7 is preferably coordinated to Ru(II), before the phosphine oxide group, which must tautomerize into the hydroxyphosphine form prior to coordination.

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

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.