Reaktionen pyrazolatoverbrueckter Dirutheniumcluster mit Diphosphanen. Synthese und Festkoerperstuktur von (μ2-H)Ru2(CO)3(μ2-η2-3,5-Me2N2C3H)2-1-η2-PPh2CH2CH2PPh(C6H4)>

Article abstract of DOI:10.1016/0022-328X(89)80034-8

The dinuclear clusters Ru2(CO)6(μ₂-η²-pz)2 und Ru2(CO)6(μ₂-η²-3,5-Me2pz)2 pz=pyrazolato) form three different types of complexes with the diphosphanes DPPM, DPPE and (1S,2S)-(+)-1,2-bis(diphenylphosphinomethyl)-cyclohexane (CYCLOP).DPPE and CYCLOP react with Ru2(CO)6(μ₂-η²-pz)2 to give the diphosphane bridged mono-substitution products Ru2(CO)4(μ₂-η²-pz)2(μ₂-η²-DPPE) (1) and Ru2(CO)4(μ₂-η²-pz)2(μ₂-η²-CYCLOP) (2).Ru2(CO)6(μ₂-η²-3,5-Me2pz)2 yields with DPPM the disubstituted product Ru2(CO)4(μ₂-η²-3,5-Me2pz)2(μ₁-η¹-DPPM)2 (3); in contrast, the coordination of DPPE and CYCLOP proceeds under ortho-metalation of one phenyl group to generate the hydrido-clusters (μ₂-H)Ru2(CO)3(μ₂-η²-3,5-Me2pz)2<μ₁-η²-PPh2XPPh(C6H4)> <4: X=CH2CH2, 5a,5b: X=CH2(C6H10)CH2>.Complex 4 crystallizes in the space group P2₁/n, a=19.185(7), b=12.113(4), c=21.547(8) Angstroem, β=115.58(3) deg.The two ruthenium atoms (Ru(1)-Ru(2): 2.898(1) Angstroem) are bridged by the two dimethylpyrazolato ligands; both phosphorus atoms are coordinated to Ru(2), while one of the aromatic rings is bonded to Ru(1).The bridging hydride ligand is localized in an almost symmetrical position between the Ru atoms.