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Functionalization of Pentaphosphorus Cations via Complexation

preprint
submitted on 16.07.2019 and posted on 17.07.2019 by Anup K. Adhikari, Christoph G. P. Ziegler, Kai Schwedtmann, clemens taube, Jan J. Weigand, Robert Wolf
The reactivity of pentaphosphorus cations [P5R2]+ (R = Cy, iPr, Mes) cations with cyclopentadienyliron, -cobalt and -nickel complexes has been investigated. Reaction of [CpArFe(µ-Br)]2 (CpAr = C5(C6H4-4-Et)5) with [P5R2][GaCl4] (R = iPr and 2,4,6-Me3C6H2 (Mes)) affords bicyclo[1.1.0]pentaphosphanes (1-R, R = iPr, Mes), showing an unsymmetrical “butterfly” structure. The same products 1-R are formed from K[CpAr] and [P5R2][GaCl4]. Cationic complexes [CpArCo(η4-P5R2)][GaCl4] (2-R[GaCl4]) and [(CpArNi)23:3-P5R2)][GaCl4] (3-R[GaCl4], R = iPr and Cy) are obtained from [P5R2][GaCl4] and [CpArM(µ-Br)]2 (M = Co, Ni) as well as by using low valent “CpArMI’’ sources. Anion metathesis of 2-R[GaCl4] and 3-R[GaCl4] was achieved with Na[BArF24] (BArF24 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate). The P5 framework of the resulting salts 2-R[BArF24] can be further functionalized with nucleophiles. Thus, reaction with [Et4N]X (X = CN, Cl) gives unprecedented chloride and cyano-functionalized complexes, while organo-functionalization was achieved with CyMgCl.

Funding

Deutsche Forschungsgemeinschaft (WE4621/3-1)

Deutsche Forschungsgemeinschaft (WO1496/7-1)

European Research Council (CoG 772299)

History

Email Address of Submitting Author

robert.wolf@ur.de

Institution

University of Regensburg, Institute of Inorganic Chemistry

Country

Germany

ORCID For Submitting Author

0000-0003-4066-6483

Declaration of Conflict of Interest

No conflict of interest to declare.

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