Mixed-d/f-metal molecular polyphosphides and related complexes

Sergey Konchenko

Nikolaev Institute of Inorganic Chemistry SB RAS

Date of Birth: September 29, 1964Place of Birth: Blagoveshchensk (USSR) Nationality: RussianEDUCATION AND ACADEMIC CAREERM.S.: Novosibirsk State University, Russia, 1986, Supervisor – Prof. A.V. Zibarev, PhD.: Nikolaev Institute of Inorganic Chemistry (NIIC), Novosibirsk, Russia, 1996, Supervisor – Dr. V.A. Maksakov, Habilitation: NIIC, Novosibirsk, Russia, 2009, "Chemistry of Cluster Complexes with Incorporated Group 16, 15 and 13 Elements"POSITIONSPermanent: NIIC, Novosibirsk, Russia, Head of research group of polynuclear metal-organic compounds.Temporary:1999-2017 (few months per year): research groups of Prof. Dr. M. Scheer (Uni-Regensburg), Prof. Dr. D. Fenske, Prof. H. Schnöckel, Prof. P.W. Roesky (KIT, Karlsruhe).

Abstract

In contrast to d-metal polyphosphide (Pn) complexes the lanthanide (Ln) ones are far less common. Their story starts from [(Cp*2Sm)4P8] obtained by reduction of P4 with [Cp*2Sm] [1]. This “reductive approach” is found to... [ view full abstract ]

In contrast to d-metal polyphosphide (P_n) complexes the lanthanide (Ln) ones are far less common. Their story starts from [(Cp*₂Sm)₄P₈] obtained by reduction of P₄ with [Cp*₂Sm] [1]. This “reductive approach” is found to be really useful for preparation of mixed d-metal/Ln P_n-complexes: the reactions of d-metal P_n-complexes with Ln(II) compounds lead to unusual transformations of P_n-ligands in the coordination sphere of metals and to formation of unprecedented mixed d-metal/Ln polyphosphides. Some examples are given in the Figure 1: the reactions (i)-(iii) illustrate different variants of dimerization of P_n units caused by transfer of electron from Sm(II), while the reaction (iv) exhibit a complicated “disproportionation” of {Mo₂P₂} moiety. The report collates results of our study focused on the reactivity of d-metal P_n-complexes towards reduction by Ln(II) compounds [2-6]. The discussion will be complemented with results of other authors and the data obtained for the heavier analogues of phosphorus [7].

Acknowledgements: This work was supported by Deutsche Forschungsgemeinschaft (DFG), Russian Science Foundation (14-23-00013), and Landesstiftung Baden-Württemberg GmbH.

[1] S. N. Konchenko, N. A. Pushkarevsky, M. T. Gamer, R. Köppe, H. Schnöckel and P. Roesky, J. Am. Chem. Soc., 2009, 131, 5740–5741.

[2] T. Li, J. Wiecko, N. A. Pushkarevsky, M. T. Gamer, R. Köppe, M. Scheer, S. N. Konchenko and P. W. Roesky, Angew. Chem., Int. Ed. Engl., 2011, 50, 9491–9495.

[3] T. Li, M. T. Gamer, M. Scheer, S. N. Konchenko and P. W. Roesky, Chem. Commun., 2013, 49, 2183–2185.

[4] T. Li, N. Arleth, M. T. Gamer, R. Köppe, T. Augenstein, F. Dielmann, M. Scheer, S. N. Konchenko and P. W. Roesky, Inorg. Chem., 2013, 52, 14231–14236.

[5] N. Arleth, M. T. Gamer, R. Köppe, S. N. Konchenko, M. Fleischmann, M. Bodensteiner, M. Scheer and P. W. Roesky, Chem. Sci., 2015, 6, 7179–7184.

[6] Ch. Schoo, S. Bestgen, M. Schmidt, S. N. Konchenko, M. Scheer, P. W. Roesky, Chem. Comm., 2016, 52, 13217–13220.

[7] See, for example: N. Arleth, M. T. Gamer, R. Köppe, S. N. Konchenko, M. Fleischmann, M. Scheer and P. W. Roesky, Angew. Chem. Int. Ed. Engl., 2016, 55, 1557-1560.

Authors

Sergey Konchenko (Nikolaev Institute of Inorganic Chemistry SB RAS)
Manfred Scheer (Regensburg University)
Peter Roesky (Karlsruhe Institute of Technology)

Topic Areas

P - Advanced synthesis and characterization , P - Reactions of coordination compounds

Session

OS2b-217a » Advanced synthesis and characterization (16:20 - Tuesday, 4th July, 217a)

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