Arleth Nicholas, Gamer Michael T, Köppe Ralf, Pushkarevsky Nikolay A, Konchenko Sergey N, Fleischmann Martin, Bodensteiner Michael, Scheer Manfred, Roesky Peter W
Institute of Inorganic Chemistry , Karlsruhe Institute of Technology , Engesserstrasse 15 , 76131 Karlsruhe , Germany . Email:
Nikolaev Institute of Inorganic Chemistry SB RAS , Novosibirsk State University , Prosp. Lavrentieva 3, Pirogova str. 2 , 630090 Novosibirsk , Russia . Email:
Chem Sci. 2015 Dec 1;6(12):7179-7184. doi: 10.1039/c5sc02252e. Epub 2015 Sep 29.
The first 4d/4f polyphosphides were obtained by reaction of the divalent metallocenes [CpLn(thf)] (Ln = Sm, Yb) with [{CpMo(CO)}(μ,η-P)] or [CpMo(CO)(η-P)]. Treatment of [CpLn(thf)] (Ln = Sm, Yb) with [{CpMo(CO)}(μ,η-P)] gave the 16-membered bicyclic compounds [(CpLn)P(CpMo(CO))] (Ln = Sm, Yb) as the major products. From the reaction involving samarocene, the cyclic P complex [(CpSm)P(CpMo(CO))] and the cyclic P complex [(CpSm)P(CpMo(CO))] were also obtained as minor products. In each reaction, the P unit is reduced and a rearrangement occurred. In dedicated cases, a P-P bond formation takes place, which results in a new aggregation of the central phosphorus scaffold. In the reactions of [CpLn(thf)] (Ln = Sm, Yb) with [CpMo(CO)P] a new P-P bond is formed by reductive dimerization and the 4d/4f hexaphosphides [(CpLn)P(CpMo(CO))] (Ln = Sm, Yb) were obtained.
通过二价茂金属化合物[CpLn(thf)]（Ln = Sm，Yb）与[{CpMo(CO)}(μ,η-P)]或[CpMo(CO)(η-P)]反应，首次制得4d/4f多磷化物。用[{CpMo(CO)}(μ,η-P)]处理[CpLn(thf)]（Ln = Sm，Yb），得到16元双环化合物[(CpLn)P(CpMo(CO))]（Ln = Sm，Yb）作为主要产物。在涉及钐茂的反应中，还得到环状磷配合物[(CpSm)P(CpMo(CO))]和环状磷配合物[(CpSm)P(CpMo(CO))]作为次要产物。在每个反应中，磷单元被还原并发生重排。在特定情况下，会形成P-P键，这导致中心磷骨架发生新的聚集。在[CpLn(thf)]（Ln = Sm，Yb）与[CpMo(CO)P]的反应中，通过还原二聚形成新的P-P键，并得到4d/4f六磷化物[(CpLn)P(CpMo(CO))]（Ln = Sm，Yb）。
