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Bis(Triphenylphosphine)Gold(I) Perrhenate

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Bis(Triphenylphosphine)Gold(I) Perrhenate Bis(triphenylphosphine)gold(I) Perrhenate Sebastian A. Baera, Alexander Pothig¨ a, Salem M. Bawakedb, Hubert Schmidbaura;b, and Florian Krausa a Department Chemie, Technische Universitat¨ Munchen,¨ 85747 Garching, Germany b Chemistry Department, King Abdulaziz University, Jeddah 21589, Saudi Arabia Reprint requests to PD Dr. F. Kraus E-mail: fl[email protected] and Prof. Dr. H. Schmidbaur [email protected] Z. Naturforsch. 2013, 68b, 1173 – 1179 / DOI: 10.5560/ZNB.2013-3223 Received August 13, 2013 Dedicated to Professor Bernd Krebs on the occasion of his 75th birthday + − Bis(triphenylphosphine)gold(I) perrhenate [Ph3PAuPPh3] ReO4 has been prepared in high yield from Ph3PAuCl, Ph3P and AgReO4 in a mixed solvent. The compound is stable in air and decomposes at 235 ◦C. In the crystal structure, the two independent perrhenate anions are not approaching the gold centers of the two independent cations, but weak interionic interactions are entertained via p-p stacking of phenyl groups and C–H···O contacts. As three-blade chiral rotors, the Ph3P ligands of the cations are in a staggered conformation at the gold atoms with only slightly bent P–Au–P axes. IR and NMR data show no anomalies and are close to those of alkali or onium perrhenates. Key words: Gold(I), Rhenate(VII), Crystal Structure, IR Spectra, Phosphine Introduction Covalently bonded perrhenates are rare and in most cases of limited stability [1–4]. This is particularly The non-coordinated tetrahedral uninegative per- true for simple perrhenic acid esters R–O–ReO3, in − rhenate anion ReO4 [1–4] is a component of many analogy to the (explosive) esters of perchloric and stable ionic solids where it appears surrounded by perbromic acid on the one hand, and of perman- a large variety of metal or onium cations [5– 18]. In ganic and pertechnetic acid on the other. An excep- solutions of these salts in protic or other polar solvents tional stability has been found, however, for silyl es- the perrhenate anion is solvated by establishing hy- ters R3SiOReO3 which can be prepared by simple drogen bonds or ion-dipole interactions, respectively. metathesis of AgReO4 with chlorosilanes R3SiCl or Owing to similar structural and charge characteristics, from siloxanes R3SiOSiR3 and Re2O7 [21]. The crys- there are many analogies not only with the correspond- tal structure of the trimethylsilyl compound (R = Me) − − ing permanganate MnO4 and pertechnetate TcO4 , has been determined [22] and shown to have a con- − but also with the perchlorate ClO4 or perbromate ventional ester structure with the Si atom attached − BrO4 anion. The similarities are so pronounced that specifically to one of the oxygen atoms in an angu- e. g. the structures of CsReO4 and CsBrO4 are isotypi- lar array. This covalent bonding has also been con- cal [19]. An increase of the coordination number of the firmed by 185;187Re NQR spectroscopy studies which rhenium(VII) center beyond 4 is observed only with showed a high asymmetry parameter h for the Re strong nucleophiles, and also in the condensation of atom, while for alkali perrhenates with largely undis- − perrhenic acid HReO4 and its hydrates Re2O7(H2O) torted ReO4 tetrahedra the h value deviates only and Re2O7(H2O)4 [20] to give the anhydride Re2O7 slightly from zero [23]. Similar characteristics have with alternating tetrahedral and octahedral coordina- later been found for the corresponding germanium [24] tion of the Re(VII) atoms [1–4]. Both perchloric or and tin compounds [25, 26], the latter being aggregated permanganic and pertechnetic acid give dinuclear an- through an increase in the coordination number of the hydrides with retention of the coordination number 4 tin atoms and with the ReO4 units functioning as bridg- of the Cl(VII), Mn(VII) and Tc(VII) atoms, respec- ing units employing two of their four oxygen atoms. tively. This work was complemented by diorganoindium and © 2013 Verlag der Zeitschrift fur¨ Naturforschung, Tubingen¨ · http://znaturforsch.com 1174 S. A. Baer et al. · Bis(triphenylphosphine)gold(I) Perrhenate other organometallic perrhenates, but structural details was separated by filtration. Addition of diethyl ether have not become available for most cases [27, 28]. to the concentrated filtrate gave a colorless precipitate These compounds are examples for the coordina- consisting of the desired product in almost quantita- − tion chemistry of the perrhenate anion (with ReO4 tive yield. Careful layering with diethyl ether allowed as a ligand), which is generally not very well devel- the growth of single crystals. The air-stable compound oped [3]. A survey of the various types of coordi- melts with decomposition at 235:4 ◦C (DSC). Elemen- nation compounds with perrhenate as a ligand shows tal analysis has confirmed the proposed composition. that there is a paucity of examples in particular for Solutions in CDCl3 show a singlet resonance at coinage metal complexes in general, and for gold com- d = 44:8 ppm in the {1H}31P NMR spectrum at 25 ◦C, plexes in particular. This situation called for some ex- and the usual complex sets of 1H and 13C resonances of ploratory experiments, because the low coordination the phenyl groups are observed in the 1H and {1H}13C number of gold(I) may offer a largely unique type of NMR spectra. The complexity of the latter is due to 0 0 0 bonding (L)Au–O–ReO3 reminiscent of the bonding in AnXX A n and BXX spin systems, respectively (A = esters of perrhenic acid R–O–ReO3 (R = alkyl, aryl, H, B = C, X = P), already observed and assigned silyl etc.). This type of bonding may also activate the also in several previous studies and not duplicated perrhenate anion for stoichiometric or catalytic reac- here [34]. The chemical shifts and coupling constants tions [29– 31]. indicate that there is no interference of the anions Surprisingly, a literature search for gold perrhen- which would distort the cations and affect these pa- ates has afforded information only for compounds rameters. of gold(III) [32, 33], but no example for gold(I). The IR spectrum of a powdered sample exhibits the The two examples with gold(III) have the metal pattern of bands characteristic of Ph3P groups attached cations chelated by two ethylenediamine (en) ligands to gold(I) atoms. The prominent band of the anion 3+ −1 in [Au(en)2] , or by one diethylenetriamine (dien) in (n3,F2, for Td symmetry) [14] appears at 900:5 cm , 2+ − [Au(dien)Cl] , and the perrhenate anions have no co- which is close to reference data for anionic ReO4 in ordinative contacts with the metal ion. the literature [35, 36]. This band is known to be rather In the present report we describe some attempts insensitive to the size and charge of innocent counter- to prepare gold(I) perrhenate complexes with tertiary ions like the alkali or alkaline earth cations (Li+–Cs+, 2+ phosphines as auxiliary ligands: R3PAu–O–ReO3. Ca ) for which its wavenumber falls in the narrow Strictly speaking, the experiments were not successful, range of 895 – 920 cm−1. The second IR-active band − but nevertheless provided us with a gold(I) perrhenate of the ReO4 anion (n4,F2) is known to be located + − −1 of the type [Au(PR3)2] ReO4 with R = Ph. near 330 cm . This region of the IR spectrum of the title compound is populated by other bands making as- Results and Discussion signments ambiguous [14]. A comparison of the solid state IR data of the ti- Attempts to prepare Ph3PAuOReO3 by metathesis tle compound with those of known metal perrhen- + − of Ph3PAuCl and AgReO4 or NH4ReO4 in a 1 : 1 molar ates M ReO4 shows that the compound has struc- ratio in various solvents and at temperatures between ture and bonding characteristics in between the ex- ◦ + − + 20 and 60 C were not successful. There was either tremes of Cs ReO4 with large and thus innocent Cs no reaction, or slow reaction led to partial decomposi- cations on the one hand and perrhenates with small and tion and formation of the impure 2 : 1 complex. There- more strongly polarizing cations (Li+, Ag+), or with + fore, the stoichiometry was changed by adding an extra cations with hydrogen bonding capabilities (NH4 ). equivalent of Ph3P: The IR spectra of the two modifications of the for- mer (a-, b-CsReO4) show the n3 band at 911 and − Ph3PAuCl + Ph3P + AgReO4 ! 913 cm 1, almost independent of temperature in the + − [(Ph3P)2Au] ReO4 + AgCl (1) range from 300 – 470 K [10]. As an example for the −1 latter, AgReO4 shows its intense n3 band at 859 cm The mixing of a solution of Ph3PAuCl and Ph3P in indicating strong cation-anion interactions. A similar I dichloromethane with a solution of AgReO4 in ace- value may be anticipated for ligand-free Au ReO4, but tonitrile gave a colorless precipitate of AgCl which this compound has not yet been prepared. By con- S. A. Baer et al. · Bis(triphenylphosphine)gold(I) Perrhenate 1175 + − Fig. 1 (color online). The two independent [Ph3PAuPPh3] and ReO4 units of the title compound. Displacement ellipsoids at the 70% probability level (at 123 K), H atoms isotropic. Two selected C-H···O contacts are shown with dashed lines. trast, [Au(en)2] (ReO4)2Cl with its ligand-covered tri- Regarding the dimensions of the perrhenate anions cation [32, 33] has this band again at 903 cm−1, the given in Table1 , a comparison with published data for −1 small shift relative to CsReO4 (910 cm ) being prob- simple reference compounds gives the following de- ably due to hydrogen bonding O···H–N to the NH2 tails: groups of the en ligand of the cation. In ionic liq- For LiReO4, the Re–O distances are in the range uids with various imidazolium cations having only 1.69 – 1.78 A˚ (average 1.716 A˚ for three different C–H···O hydrogen bonding capabilities, the n3 band anions) [7].
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