Nickelate, complex with water soluble phosphine

Nickel(0) complexes with water-soluble phosphines have attracted interest in the context of homogeneous catalysis. A comprehensive study of the coordination chemistry of tris(sodium-m-sulfonatophenyl)phosphine (1039) has appeared.2504 The complexes [Ni(CO)2(1039)2] 6HzO have been made by reaction of (1039) with Ni(CO)4 under phase-transfer conditions, and the homo-leptic [Ni(1039)3]-9H2O has been made from Ni° precursors and (1039) under phase-transfer conditions, or from NiCl2, (1039), and BH4 in water. A related complex [Ni(CO)2(1040)2] with the bidentate ligand (1040) has also been studied.2505... 

The linear telomerization reaction of dienes was one of the very first processes catalyzed by water soluble phosphine complexes in aqueous media [7,8]. The reaction itself is the dimerization of a diene coupled with a simultaneous nucleophilic addition of HX (water, alcohols, amines, carboxylic acids, active methylene compounds, etc.) (Scheme 7.3). It is catalyzed by nickel- and palladium complexes of which palladium catalysts are substantially more active. In organic solutions [Pd(OAc)2] + PPhs gives the simplest catalyst combination and Ni/IPPTS and Pd/TPPTS were suggested for mnning the telomerizations in aqueous/organic biphasic systems [7]. An aqueous solvent would seem a straightforward choice for telomerization of dienes with water (the so-called hydrodimerization). In fact, the possibility of separation of the products and the catalyst without a need for distillation is a more important reason in this case, too. 

Miscellaneous Reactions of Phosphines.- The role of chiral phosphines as ligands in the catalysis of reactions leading to the formation of chiral products has been reviewed.1111 A procedure for the determination of the enantiomeric excess in chiral phosphines has been developed, based on 13C n.m.r. studies of the diastereoisomeric complexes formed by phosphines with the chiral pinenyl nickel bromide complex. 111 Studies of the sulphonation of triphenylphosphine and of chiral arylphosphines have been reported in attempts to prepare water soluble ligands which aid... 

Ellis, J.W., Harrison, K.N., Hoye, P.A.T., Orpen, A.G., Pringle, P.G., and Smith, M.B., Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium, and platinum. Crystal structure of Pd P(CH2OH)3 4].cntdot.CH3, Inorg. Chem., 31, 3026, 1992. 

Bartik, T. Bunn, B.B. Bartik, B. Hanson, B.E. (1994) Synthesis, reactions, and catalytic chemistry of the water-soluble chelating phosphine l,2-bis[bis(m-sodiosulfonatophenyl)-phosphinojethane (dppets) complexes with nickel, palladium, platinum, and rhodium, Inorg. Chem., 33, 164-9. 

Cross-coupling. Suzuki coupling tolerable to water is achieved using the phosphine-free complex (ELN)2NiCl2. A soluble nickel species prepared from treatment of Ph3P and NiCl2 with BuLi effects the coupling of RZnI with ArCl. ... 

---