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)
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)
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DOI：
10.1021/om9602320
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发表时间：
1996-10-01
期刊：
影响因子：
2.8
通讯作者：
Ricard, L
中科院分区：
文献类型：
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作者：
Desmurs, P;Visseaux, M;Ricard, L
首次合成了具有桥联磷基配体的异质双金属锆Ru和Yb Ru二氢化合物。Bin(eta(5)-tetramethylphospholyl)dichlorozirconium[(TMP)(2)ZrCl2]与RuH4(PPh(3))(3)反应，得到了双金属化合物Cl2Zr[Mu(EtA(5)，EtA(1))-TMP]Ru-2(H)(2)(PPh(3))(2)。在CCl4的作用下，该化合物转变为氯化氢Cl2Zr[Mu(ETA(5)，ETA(1))-TMP]Ru-2(H)(Cl)(PPh(3))(2)。类似地，[(TMP)(2)Yb]与RuH4(PPh(3))(3)反应得到(THF)(2)Yb[Mu(ETA(5)，ETA(1))-TMP]Ru-2(H)(2)(PPh(3))(2)。该化合物的结构已由X-射线结晶学确定，证实了先前从核磁共振数据推导出的二氢化物的反式构型。试图从[(TMP)(2)UCl2]或[(TMP)(2)U(BH4)(2)]与RuH4(PPh(3))(3)反应中分离产物的尝试失败了，但核磁共振数据显示在溶液中形成了异双金属的反式和顺式双金属二氢化铀化合物X(2)U[Mu(ETA(5)，ETA(1)-TMP]Ru-2(H)(2)(PPh(3))(2)(X=BH4，Cl))。
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.