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Functionalization of Pentaphosphorus Cations via Complexation

submitted on 16.07.2019, 22:14 and posted on 17.07.2019, 18:54 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.


Deutsche Forschungsgemeinschaft (WE4621/3-1)

Deutsche Forschungsgemeinschaft (WO1496/7-1)

European Research Council (CoG 772299)


Email Address of Submitting Author


University of Regensburg, Institute of Inorganic Chemistry



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest to declare.