Synthesis of phospholyl-bridged heterobimetallic ruthenium hydrides in combination with zirconium and ytterbium and the crystal structure of (THF)(2)Yb[mu(eta(5),eta(1))-C(4)Me(4)P]Ru-2(H)(2)(Ph(3)P)(2)

Heterobimetallic zirconium-ruthenium and ytterbium-ruthenium dihydrides, having bridging phospholyl ligands, have been obtained for the first time. Reaction of bin(eta(5)-tetramethylphospholyl)dichlorozirconium [(TMP)(2)ZrCl2] with RuH4(PPh(3))(3) gave the zirconium-ruthenium heterobimetallic Cl2Zr[mu(eta(5),eta(1))-TMP]Ru-2(H)(2)(PPh(3))(2). This compound was transformed into the hydridochloride Cl2Zr[mu(eta(5),eta(1))-TMP]Ru-2(H)(Cl)(PPh(3))(2) by the action of CCl4. Similarly, reaction of [(TMP)(2)Yb] with RuH4(PPh(3))(3) afforded (THF)(2)Yb[mu(eta(5),eta(1))-TMP]Ru-2(H)(2)(PPh(3))(2). The structure of this compound, which has been determined by X-ray crystallography, confirms the trans configuration of the dihydride deduced previously from NMR data. Attempts to isolate products from the reaction of [(TMP)(2)UCl2] or [(TMP)(2)U(BH4)(2)] with RuH4(PPh(3))(3) were unsuccessful, but NMR data show the formation of both heterobimetallic trans- and cis-ruthenium dihydride-uranium compounds X(2)U[mu(eta(5),eta(1))-TMP]Ru-2(H)(2)(PPh(3))(2) (X = BH4, Cl) in solution.