Dichlorido(η6-p-cymene)[tris(2-cyanoethyl)phosphine]ruthenium(II)

Ashwin Nair,Nathan Halcovich,William Henderson,Edward Tiekink

doi:10.3390/m1025

Ashwin Nair, Nathan Halcovich + Show 2 more

Open Access

https://doi.org/10.3390/m1025

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Abstract

The tris(2-cyanoethyl)phosphine (tcep) complex [RuCl2{P(CH2CH2CN)3}(η6-p-cymene)] (p-cymene = p-CH3C6H4iPr) was synthesised by the bridge-splitting reaction of the chlorido-dimer [RuCl2(η6-p-cymene)]2 with tcep. The complex was characterised by a single-crystal X-ray structure determination as well as NMR spectroscopy, ESI mass spectrometry, and microelemental analysis. X-ray crystallography shows the ruthenium atom is coordinated by p-cymene in a η6-fashion, two chlorides and the phosphorus atom of the tcep ligand with the donor set defining a distorted octahedral geometry. The ESI mass spectrometry study reveals that the complex readily forms negative ions [M + Cl]− and [2M + Cl]− by association with a chloride ion.

Highlights

Tris(2-cyanoethyl)phosphine, P(CH2 CH2 CN)3, is an interesting ligand on account of its simple synthesis [1] from commercially available [P(CH2 OH)4 ]Cl and acrylonitrile, and its user-friendly properties; it is, unlike the majority of tertiary alkylphosphines, crystalline and air-stable
There have been a number of studies on the coordination chemistry of this ligand [4], towards transition metal centres, such as palladium and platinum [5,6,7] and gold [8]
Relatively few ruthenium complexes of this ligand have been investigated to date [9,10,11,12,13]

Summary

Introduction

Tris(2-cyanoethyl)phosphine, P(CH2 CH2 CN) (tcep), is an interesting ligand on account of its simple synthesis [1] from commercially available [P(CH2 OH)4 ]Cl and acrylonitrile, and its user-friendly properties; it is, unlike the majority of tertiary alkylphosphines, crystalline and air-stable. Its stereoelectronic properties have attracted interest on account of its relatively small cone angle, that is, 132◦ [2,3]. Relatively few ruthenium complexes of this ligand have been investigated to date [9,10,11,12,13]. The only examples of ruthenium π-hydrocarbon derivatives include the complexes [Ru(η 5 -C5 H4 R)Cl(tcep)2 ] (R = H, CH3 , CH3 CO) formed by reaction of [Ru(η 5 -C5 H4 R)Cl(PPh3 )2 ] with excess tcep in toluene [14]. In recognition of the above, the synthesis, spectroscopic characterisation and X-ray crystal structure determination of the title complex, 1, Scheme 1, are described

Results

The in the the crystal crystal of of 1

General Information

Crystallography