Laura Crociani

Telomerization of butadiene with methanol catalysed by cationic palladium complexes containing a bidentate phosphinoamino ligand

Abstract The cationic complexes [Pd(η 3 -allyl){Ph 2 P( o -C 6 H 4 NMe 2 )}]PF 6 ( 1 ) and [PdMe(PPh 3 ){Ph 2 P( o -C 6 H 4 NMe 2 )}]CF 3 SO 3 ·C 6 H 6 ( 2 ) catalyse, without any added phosphine, the telomerization reaction of 1,3-butadiene with methanol, showing high chemio- (>95%) and regioselectivity towards the linear 1-methoxy-2,7-octadiene (>93%).

Phosphinoamino complexes of copper(I) and silver(I): a combined NMR and IR spectroscopy, and electrospray ionization and fast atom bombardment mass spectrometry analysis

Abstract Bidentate ‘PN’ and tetradentate ‘P2N2’ ligands from stable silver(1) complexes, which were characterized by NMR and IR spectroscopy. Conductivity measurements indicate an ionic nature of the compounds in solution. A thorough mass spectrometric study (electrospray ionization and fast atom bombardment) of these complexes and the corresponding Cu(1) analogues supports the NMR and IR structural information.

The relationship between electrospray ionization behavior and cytotoxic activity of [MI(P)4]+‐type complexes (M = Cu, Ag and Au; P = tertiary phosphine)

RATIONALE To try to find a correlation between the antiproliferative activity of a series of [M(I)(P)4](+) complexes (M = Cu, Ag and Au; P = tertiary phosphine) and their stability at micromolar concentration under mass spectrometric conditions. METHODS [M(I)(P)4](+) complexes were investigated by positive ion electrospray ionization mass spectrometry with multiple collisional experiments using an ion trap mass spectrometer. RESULTS The displacement of P from native [M(I)(P)4](+), previously described for the copper derivative, is common for the triad complexes leading to the formation of [M(P)3](+) and [M(P)2](+) adducts. Further dissociation of [M(P)2](+) depends on the nature of the metal (Cu ~ Ag > Au). More labile [Cu(P)2](+) and [Ag(P)2](+) are more cytotoxic against HCT-15 human colon carcinoma cells compared to less labile [Au(P)2](+) species. CONCLUSIONS The dissociation of P ligand(s) from the [M(I)(P)4](+) complexes is the driving force for the triggering of the antiproliferative activity. The more favored is the displacement of P from the [M(P)2](+) active form, the more favored is in turn the possibility for the metal to interact with biological substrates related to cancer proliferation.

Neutral and cationic nickel(II) complexes of phosphino-amines: [NiCl2(PMe2Ph) (PNMe2)] and [NiCl(PMe2Ph) (PNMe2)] PF6 (PNMe2 = N,N′-dimethyl-2-(diphenylphosphino)aniline)

A neutral bidentate P,N-ligand combining a hard dimethylamino nitrogen and a soft phosphine phosphorus donor affords the neutral trigonal bipyramidal as well as the cationic square-planar nickel(II) complexes cis-[NiCl2(PMe2Ph)(PNMe2)] and [NiCl(PMe2Ph)(PNMe2)]PF 6, respectively. The latter species exhibits an appreciable catalytic activity in propylene oligomerization in the presence of Et2AlCl as co-catalyst

Phosphanyl-Amino Complexes of Nickel(II): Synthesis and Structure

New neutral pentacoordinate nickel(II) complexes of the type [NiCl2(PR3)(P∩N)] [PR3 = PMe3, PMe2Ph, PMePh2; P∩N = 2-(diphenylphosphanyl)aniline (P∩NH2), N-methyl-2-(diphenylphosphanyl)aniline (P∩NHMe), N,N-dimethyl-2-(diphenylphosphanyl)aniline (P∩NMe2)], as well as cationic tetracoordinate nickel(II) complexes of the type [NiCl(PR3)(P∩N)]+ have been synthesized and characterized both in the solid state and in solution. Interesting X-ray structural data have been collected for each class of compounds, which show, inter alia, that the pentacoordinate neutral complexes can be isolated in two different molecular forms, namely square-pyramidal or bipyramidal-trigonal.