Stabilization of the P(CF(3))(2)(-) ion as a reversible CS(2) adduct, [P(CF(3))(2)CS(2)](-), and its potential use as a nucleophilic P(CF(3))(2)(-) source: synthesis and structure of [18-crown-6-K][P(C(6)F(5))(2)CS(2)]

Berthold Hoge; Christoph Thösen; Tobias Herrmann; Ingo Pantenburg

doi:10.1021/ic0112950

Stabilization of the P(CF(3))(2)(-) ion as a reversible CS(2) adduct, [P(CF(3))(2)CS(2)](-), and its potential use as a nucleophilic P(CF(3))(2)(-) source: synthesis and structure of [18-crown-6-K][P(C(6)F(5))(2)CS(2)]

Inorg Chem. 2002 Apr 22;41(8):2260-5. doi: 10.1021/ic0112950.

Authors

Berthold Hoge¹, Christoph Thösen, Tobias Herrmann, Ingo Pantenburg

Affiliation

¹ Institut für Anorganische Chemie, Universität zu Köln, D-50939 Köln, Germany. b.hoge@uni-koeln.de

PMID: 11952383
DOI: 10.1021/ic0112950

Abstract

The bis(trifluoromethyl)phosphanide ion, P(CF(3))(2)(-), decomposes slowly above -30 degrees C in CH(2)Cl(2) and THF solution. An increase of the thermal stability of the P(CF(3))(2)(-) moiety is observed if excess CS(2) is added. The P(CF(3))(2)(-) moiety is stabilized because of the formation of the bis(trifluoromethyl)phosphanodithioformate anion. Solutions of a [P(CF(3))(2)CS(2)](-) salt still act as a source of P(CF(3))(2)(-), even in the presence of excess of CS(2). The stable compound [18-crown-6-K][P(CF(3))(2)CS(2)] was characterized by multinuclear NMR spectroscopy, elemental analysis, and vibrational spectroscopy in combination with quantum chemical calculations. The thermally unstable P(C(6)F(5))(2)(-) ion decomposes even at -78 degrees C in solution giving polymeric material. The intermediate formation of the bis(pentafluorophenyl)phosphanide anion in the presence of excess of CS(2) allows the isolation of [18-crown-6-K][P(C(6)F(5))(2)CS(2)]. The novel compound crystallizes with one solvent molecule CH(2)Cl(2) in the monoclinic space group P2(1)/n with a = 1151.8(1) pm, b = 1498.1(2) pm, c = 2018.2(2) pm, beta = 102.58(1) degrees, and Z = 4. Optimized geometric parameters of the [P(C(6)F(5))(2)CS(2)](-) ion at the B3PW91/6-311G(d) level of theory are in excellent agreement with the experimental values.