Di-, tetra- and polynuclear RhI complexes containing phenylene-1,4-diaminotetra (phosphonite), p-C6H4[N{P(OC6H4OMe-o)2}2]2 and their catalytic investigation towards transfer hydrogenation reactions.

The reactions of phenylene-1,4-diaminotetra(phosphonite), p-C(6)H(4)[N{P(OC(6)H(4)OMe-o)(2)}(2)](2) (P(2)N(Ph)NP(2)) () with [Rh(COD)Cl](2) in 1 : 2 and 1 : 1 molar ratio produce tetra- and polymetallic chelate complexes, [Rh(4)(COD)(2)(micro-Cl)(4)(P(2)N(Ph)NP(2))] () and [Rh(2)(micro-Cl)(2)(P(2)N(Ph)NP(2))](n) (), respectively. Similar reaction of with [Rh(COD)Cl](2) in dichloromethane-acetonitrile mixture furnishes a dinuclear complex, [Rh(2)Cl(2)(CH(3)CN)(2)(P(2)N(Ph)NP(2))] (). The reaction of or with CO affords a dinuclear carbonyl derivative, [Rh(2)Cl(2)(CO)(2)(P(2)N(Ph)NP(2))] (). Treatment of with 2 equivalents of pyrazine or 4,4'-bipyridine produce one-dimensional Rh(I) coordination polymers, [Rh(2)Cl(2)(C(4)H(4)N(2))(P(2)N(Ph)NP(2))](n) () and [Rh(2)Cl(2)(C(10)H(8)N(2))(P(2)N(Ph)NP(2))](n) in quantitative yields. The catalytic activity of Rh(I) complexes have been investigated in transfer hydrogenation reactions.