The approach to 4d/4f-polyphosphides
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| Authors: | Nicholas Arleth Michael T Gamer Ralf K?ppe Nikolay A Pushkarevsky Sergey N Konchenko Martin Fleischmann Michael Bodensteiner Manfred Scheer Peter W Roesky |
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| Institution: | a Institute of Inorganic Chemistry , Karlsruhe Institute of Technology , Engesserstrasse 15 , 76131 Karlsruhe , Germany . Email: ; b Nikolaev Institute of Inorganic Chemistry SB RAS , Novosibirsk State University , Prosp. Lavrentieva 3, Pirogova str. 2 , 630090 Novosibirsk , Russia . Email: ; c Institute of Inorganic Chemistry , University of Regensburg , 93040 Regensburg , Germany . Email: |
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| Abstract: | The first 4d/4f polyphosphides were obtained by reaction of the divalent metallocenes Cp*2Ln(thf)2] (Ln = Sm, Yb) with {CpMo(CO)2}2(μ,η2:2-P2)] or Cp*Mo(CO)2(η3-P3)]. Treatment of Cp*2Ln(thf)2] (Ln = Sm, Yb) with {CpMo(CO)2}2(μ,η2:2-P2)] gave the 16-membered bicyclic compounds (Cp2*Ln)2P2(CpMo(CO)2)4] (Ln = Sm, Yb) as the major products. From the reaction involving samarocene, the cyclic P4 complex (Cp*2Sm)2P4(CpMo(CO)2)2] and the cyclic P5 complex (Cp*2Sm)3P5(CpMo(CO)2)3] were also obtained as minor products. In each reaction, the P2 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 Cp*2Ln(thf)2] (Ln = Sm, Yb) with Cp*Mo(CO)2P3] a new P–P bond is formed by reductive dimerization and the 4d/4f hexaphosphides (Cp*2Ln)2P6(Cp*Mo(CO)2)2] (Ln = Sm, Yb) were obtained. |
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