Synthesis, Characterization, and Electrochemical Properties of Novel Transition Metal–Fullerene Complexes Containing Di‐ and Tetraphosphane Ligands

Abstract

This paper reports the synthesis, characterization, and some properties of transition metal–fullerene complexes containing trans‐1,1′‐bis(diphenylphosphanyl)ethylene (dppet, trans‐Ph2PCH=CHPPh2) and N,N,N′,N′‐tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda, [(Ph2PCH2)2NCH2]2), including [(η2‐C60M)(dppet)2] (M = Pt 1, Pd 2), [(η2‐C60M)(dppet)]2 (M = Pt 3, Pd 4), [(η2‐C60Pd)(η2‐C60Pt)(dppet)2](5), [(η2‐C60Pd)(η2‐C70Pd)(dppet)2] (6), [(η2‐C70Pd)(dppet)]2 (7), [(η2‐C60M)(dppeda)] (M = Pt 8, Pd 9), and [(η2‐C60M)2(dppeda)] (M = Pt 10, Pd 11). Interestingly, while complexes 1, 2, 8, and 9 are the first examples of metallacyclopropafullerene diphosphane ligands containing fullerene cores, complexes 3–7, 10, and 11 are the first group 10 metal‐containing, dumbbell‐shaped bisfullerenes. All the complexes 1–11 were characterized by elemental analysis, spectroscopy, and, particularly for 4 and 5, by X‐ray crystallography and cyclic voltammetry. Pathways for the formation of 1–11 are suggested. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R2PCH2OH

“…Compounds of the formula (R 2 PCH 2 ) 2 N(R) and {(R 2 PCH 2 ) 2 N} 2 (R) are two such examples [6][7][8][9][10] which have interesting coordination properties, catalytic applications and, more recently, are important ligands for self-assembly reactions using covalent bonds or H-bonding interactions.…”

Fullerenes

“…130 Novel transition metal-fullerene complexes containing diand tetra-phosphane ligands have been obtained, characterized and their electrochemical properties have been described. 131 For providing a simple model of natural photosynthesis, two novel ruthenocene-C 60 dyads, with a 2-pyrazoline or a pyrrolidine rings as a linker, have been synthesized and characterized. It has been found that ruthenocene- [60]fullerenes have an ability to prolong the charge-separated states compared with those for ferrocene- [60]fullerenes.…”

Two 1D [CuxIx]-based coordination polymers of tetraphosphine ligands

“…Among the multiphosphine ligands, several tetraphosphine ligands and their metal complexes that showed interesting luminescent properties, catalytic and anticancer performances, have been extensively investigated [17][18][19][20]. In the case of IB metals, the tetraphosphine ligands could react with Au(I) and Ag(I) salts to form luminescent Au(I) complexes [20] and Ag(I) complexes (cage-like) [11][12][13].…”

“…Relative to the -CH 2 CH 2 -spacer in dppeda, the phenyl spacer in dpppda is longer and more rigid. Therefore, dppeda in 1 has a smaller side-space and takes a l-g 2 :g 2 end-to-end mode (Scheme 1) [17][18][19][20][21] to chelate at each of the two Cu atoms of the [Cu 2 I 2 ] core via two Cu-P bonds. On the contrary, dpppda in 2 adopts a rare Z-shaped l-g 2 :g 2 side-by-side mode (Scheme 1) to have more side-space to coordinate at the four Cu(I) centers of the [Cu 4 I 4 ] core via four Cu-P bonds.…”