Transition Metal Chemistry of Main Group Hydrazides. 16. (Phosphanyl)hydrazines R2PN(Me)N(Me)PR2 as a Novel Class of Chelating Bis(phosphines).Synthesis, Coordination Chemistry, and X-ray Structure of cis-[PdCl2{(p-BrC6H4O)2PN(Me)N(Me)P(OC6H4Br-p)2}] and ...

Article abstract of DOI:10.1021/ic00126a018

The alkoxy- and aryloxy-functionalized bis(phosphanyl)hydrazines of thetype (OR)2PN(Me)N(Me)P(OR)2 were obtained from the reactions of the corresponding alcohols and phenols with Cl2PN(Me)N(Me)PCl2 in the presence of Et3N. Interaction of these ligands with group 6 metal carbonyl precursors M(CO)4(NHC5H10)2 (M = Mo, W) gave the tetracarbonyl complexes of the type cis-[M(CO)4(OR)2PN(Me)N(Me)P(OR)2}]. The reactions of the alkoxy and aryloxy-functionalized bis(phosphanyl)hydrazines with Pd(PhCN)2Cl2 or with Pt(COD)Cl2 resulted in the formation of the complexes of the typecis-[MCl2(OR)2PN(Me)N(Me)P(OR)2}]. The ligands are bound cis to the metal center(s) in all the complexes. The structures of all the complexes have been established by combination of spectroscopic and elemental analysis. As representative examples, we have determined the structures of cis-[W(CO)4{(OPh)2PN(Me)N(Me)P(OPh)2}] (15) and cis-[PdCl2{(OC6H4Br-p)2PN(Me)N(Me)P(OC6H4Br-p)2}] (19) by X-ray crystallography. X-ray data for 15: monoclinic, P21/n, a = 13.419(5) ?, b = 19.588(3) ?, c = 12.253(3) ?, β = 103.65(2)°, Z = 4, and R = 0.025 (Rw = 0.033). X-ray data for 19: triclinic, P1-, a = 9.252(3) ?, b = 9.882(3) ?, c = 17.739(5) ?, α = 83.84(2)°, β = 83.98(2)°, γ = 84.45(2)°, Z = 2, and R = 0.064 (Rw = 0.076).