NEW MIXED-LIGAND ISOCYANIDE DIPHOSPHINE RUTHENIUM(II) DERIVATIVES - SYNTHESIS OF A POTENTIAL METAL-CONTAINING TETRADENTATE LIGAND

Reaction of trans-[RuCl2(CNPh)(4)] with an excess of Ph(2)PCH(2)PPh(2) (dppm) in refluxing toluene gave two complexes cis,cis,trans-[RUCl(2)(CNPh)(2)(dppm-P)(2)] 1 and mer- [RuCl(CNPh)(3)(dppm)]Cl 2a; whereas in the reaction of trans-[RuCl2(CNBu(t))(4)] with dppm under the same conditions only mer-[RuCl-(CNBu(t))(3)(dppm)]Cl 2b was obtained. Complex 1 reacted with TlPF6 in CH2Cl2 to give [RuCl(CNPh)(2)(dppm) (dppm-P)]PF6 3, a cationic complex containing both a monodentate and a chelated dppm ligand. Complex 1 is remarkable in having two monohapto dppm ligands and can be used in the synthesis of heterometallic species. Thus, treatment of 1 with AgClO4 or HgCl2 gave the heterometallic complex [(dppm)(PhNC)(2)ClRu(mu-dppm)AgCl]ClO4 4 or [{(dppm)(PhNC)(2)ClRu-(mu-dppm)HgCl2}(2)] Cl-2 5 respectively.