Abstract
The previously unknown dianions [H6Cl4O2]2− and [H6Br4O2]2− were prepared as their bis(triphenyl-λ5-phosphanylidene)ammonium ([Ph3PNPPh3]+ ≡ [PNP]+) salts from [PNP]+ halides and aqueous hydrochloric or hydrobromic acid, respectively. The crystal structures of the two salts [PNP]2[H6Cl4O2] and [PNP]2[H6Br4O2] are reported. The unprecedented dianions [H6Cl4O2]2− and [H6Br4O2]2−, which represent a section of the structure of halide-rich hydrochloric or hydrobromic acid, are discussed. Quantum-chemical calculations support the findings. The crystal structure of [PNP][HBr2], a rare example for a crystallographically determined hydrogen dibromide structure, is presented as well.
Graphical Abstract
The dianions [H6Cl4O2]2− and [H6Br4O2]2− were prepared as their [PNP]+ salts and structurally characterized.
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References
Yoon YK, Carpenter GB (1959) The crystal structure of hydrogen chloride monohydrate. Acta Crystallogr 12(1):17–20
Lundgren JO, Olovsson I (1967) Hydrogen bond studies. XV. The crystal structure of hydrogen chloride dihydrate. Acta Crystallogr 23(6):966–971
Lundgren JO, Olovsson I (1967) Hydrogen bond studies. XVI. The crystal structure of chloride trihydrate. Acta Crystallogr 23(6):971–976
Taesler I, Lundgren JO (1978) Hydrogen bond studies. CXXIX. An X-ray determination of the crystal structure of hydrogen chloride hexahydrate, H9O4+Cl–.2H2O. Acta Crystallogr B 34(8):2424–2428
Baer MD, Fulton JL, Balasubramanian M, Schenter GK, Mundy CJ (2014) Persistent ion pairing in aqueous hydrochloric acid. J Phys Chem B 118(26):7211–7220
Fulton JL, Balasubramanian M (2010) Structure of hydronium (H3O+)/chloride (Cl–) contact ion pairs in aqueous hydrochloric acid solution: a Zundel-like local configuration. J Am Chem Soc 132(36):12597–12604
Xu J, Izvekov S, Voth GA (2010) Structure and dynamics of concentrated hydrochloric acid solutions. J Phys Chem B 114(29):9555–9562
Kovács A, Varga Z (2006) Halogen acceptors in hydrogen bonding. Coord Chem Rev 250(5):710–727
Jeffrey GA (2003) Hydrogen-bonding: an update. Crystallogr Rev 9(2–3):135–176
Arunan E, Desiraju GR, Klein RA, Sadlej J, Scheiner S, Alkorta I, Clary DC, Crabtree RH, Dannenberg JJ, Hobza P, Kjaergaard HG, Legon AC, Mennucci B, Nesbitt DJ (2011) Defining the hydrogen bond: an account (IUPAC technical report). Pure Appl Chem 83(8):1619–1636
Emsley J (1980) Very strong hydrogen bonding. Chem Soc Rev 9(1):91–124
Grabowski SJ (2011) What is the covalency of hydrogen bonding? Chem Rev 111(4):2597–2625
Kemp DD, Gordon MS (2010) Aqueous solvation of bihalide anions. J Phys Chem A 114(3):1298–1303
Landrum A, Goldberg G, Hoffmann N R (1997) Bonding in the trihalides (X3–), mixed trihalides (X2Y–) and hydrogen bihalides (X2H–). The connection between hypervalent, electron-rich three-center, donor-acceptor and strong hydrogen bonding. J Chem Soc Dalton Trans 19:3605–3613
Caldwell G, Kebarle P (1985) The hydrogen bond energies of the bihalide ions XHX– and YHX–. Can J Chem 63(7):1399–1406
Pivonka NL, Kaposta C, Brümmer M, von Helden G, Meijer G, Wöste L, Neumark DM, Asmis KR (2003) Probing a strong hydrogen bond with infrared spectroscopy: vibrational predissociation of BrHBr–·Ar. J Chem Phys 118(12):5275–5278
Pivonka NL, Kaposta C, von Helden G, Meijer G, Wöste L, Neumark DM, Asmis KR (2002) Gas phase infrared spectroscopy of cluster anions as a function of size: the effect of solvation on hydrogen-bonding in Br–·(HBr)1,2,3 clusters. J Chem Phys 117(14):6493–6499
Ault BS (1982) Matrix isolation investigation of the hydrogen bihalide anions. Acc Chem Res 15(4):103–109
Grabowski SJ, Ugalde JM, Andrada DM, Frenking G (2016) Comparison of hydrogen and gold bonding in [XHX]–, [XAuX]−, and Isoelectronic [NgHNg]+, [NgAuNg]+ (X = halogen, Ng = noble gas). Chem Eur J 22(32):11317–11328
Groom CR, Bruno IJ, Lightfoot MP, Ward SC (2016) The cambridge structural database. Acta Crystallogr B 72:171–179
Farnham WB, Dixon DA, Middleton WJ, Calabrese JC, Harlow RL, Whitney JF, Jones GA, Guggenberger LJ (1987) The crystal and molecular structure of tris(substituted amino) sulfonium ions. J Am Chem Soc 109(2):476–483
Lork E, Viets D, Müller M, Mews R (2004) Bis(dimethylamino)trifluoromethylsulfonium salze: [CF3S(NMe2)2]+[Me3SiF2]–, [CF3S(NMe2)2]+[HF2]– und [CF3S(NMe2)2]+[CF3S]. Z Anorg Allg Chem 630(15):2692–2696
Troyanov SI, Morozov IV, Kemnitz E (2005) Crystal structure of cesium dihydrotrifluoride, CsH2F3. Refinement of the crystal structures of NMe4HF2 and NMe4H2F3. Z Anorg Allg Chem 631(9):1651–1654
Atwood JL, Bott SG, Means CM, Coleman AW, Zhang H, May MT (1990) Synthesis of salts of the hydrogen dichloride anion in aromatic solvents. 2. Syntheses and crystal structures of [K·18-crown-6][Cl-H-Cl], [Mg·18-crown-6][Cl-H-Cl]2, [H3O·18-crown-6][Cl-H-Cl], and the related [H3O·18-crown-6][Br-H-Br]. Inorg Chem 29(3):467–470
Bertocco P, Bolli C, Correia Bicho BA, Jenne C, Erken B, Laitinen RS, Seeger HA, Takaluoma TT (2016) Theoretical and synthetic study on the existence, structures, and bonding of the halide-bridged [B2X7]– (X = F, Cl, Br, I) anions. Inorg Chem 55(7):3599–3604
Paul USD, Radius U (2017) Ligand versus complex: C–F and C–H bond activation of polyfluoroaromatics at a cyclic (Alkyl)(Amino)carbene. Chem Eur J 23(16):3993–4009
Müller U, Dörner H-D (1982) Eine neue Synthese, das Schwingungsspektrum und die Kristallstruktur von Tetraphenylarsonium-hydrogendichlorid As(C6H5)4[Cl2H]. Z Naturforsch 37B(2):198–200
Schroeder LW, Ibers JA (1968) Bihalide ions ClHCl– and BrHBr–. Crystal structures of cesium chloride-1/3-(hydronium bichloride) and cesium bromide-1/3-(hydronium bromide). Inorg Chem 7(3):594–599
Driver GW, Mutikainen I (2011) The complex story of a simple bronsted acid: unusual speciation of HBr in an ionic liquid medium. Dalton Trans 40(41):10801–10803
Gellhaar J, Knapp C (2011) Bis(triphenyl-λ5-phosphanylidene)ammonium hydrogen dichloride. Acta Crystallogr Sect E 67(10):o2546
Knapp C, Uzun R (2010) Bis(triphenylphosphine)iminium bromide acetonitrile monosolvate. Acta Crystallogr E 66:o3186
Knapp C, Uzun R (2010) Solvate-free bis(triphenylphosphine)iminium chloride. Acta Crystallogr E 66:o3185
Bolli C, Gellhaar J, Jenne C, Keßler M, Scherer H, Seeger H, Uzun R (2014) Bis (triphenyl-λ5-phosphanylidene) ammonium fluoride: a reactive fluoride source to access the hypervalent silicates [MenSiF5−n]- (n= 0–3). Dalton Trans 43(11):4326–4334
Price CJ, Chen H-Y, Launer LM, Miller SA (2009) Weakly coordinating cations as alternatives to weakly coordinating anions. Angew Chem Int Ed 48(5):956–959
Zhang B, Li S, Cokoja M, Herdtweck E, Mink J, Zang S-L, Herrmann WA, Kühn FE (2014) Ion pairs of weakly coordinating cations and anions: synthesis and application for sulfide to sulfoxide oxidations. Z Naturforsch 69B(11–12):1149–1163
Mann L, Hornberger E, Steinhauer S, Riedel S (2018) Further development of weakly coordinating cations: fluorinated Bis(triarylphosphoranylidene)iminium salts. Chem Eur J 24(15):3902–3908
Himmel D, Goll SK, Leito I, Krossing I (2012) Bulk gas-phase acidity. Chem Eur J 18(30):9333–9340
Botti A, Bruni F, Imberti S, Ricci MA, Soper AK (2004) Ions in water: the microscopic structure of a concentrated HCl solution. J Chem Phys 121(16):7840–7848
Agmon N (1998) Structure of Concentrated HCl Solutions. J Phys Chem A 102(1):192–199
Martinsen A, Songstad J (1977) Preparation and properties of some Bis(triphenylphosphine)iminium salts, [(Ph3P)2N]X. Acta Chem Scand 31A:645–650
Sheldrick GM (2008) A short history of SHELX. Acta Crystallogr A 64(1):112–122
Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H (2009) OLEX2: a complete structure solution, refinement and analysis program. J Appl Crystallogr 42(2):339–341
Sheldrick G (2015) Crystal structure refinement with SHELXL. Acta Crystallogr C 71(1):3–8
Adamo C, Barone V (1999) Toward reliable density functional methods without adjustable parameters: the PBE0 model. J Chem Phys 110(13):6158–6170
Weigend F, Ahlrichs R (2005) Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys Chem Chem Phys 7(18):3297–3305
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ (2016) Gaussian 16 Rev. A.03. Wallingford, CT
Chemcraft—graphical software for visualization of quantum chemistry computations. Retrieved from https://www.chemcraftprog.com
Tebbe KF, Krauss N (1990) Bis(triphenylphosphin)iminium-triiodid. Acta Crystallogr C 46(5):878–880
Lewis GR, Dance I (2000) Crystal supramolecularity. Multiple phenyl embraces by [PPN]+ cations. J Chem Soc Dalton Trans (3):299–306
Schröder D (2004) Coulomb explosions and stability of multiply charged ions in the gas phase. Angew Chem Int Ed 43(11):1329–1331
Knapp C, Schulz C (2009) How to overcome Coulomb explosions in labile dications by using the [B12Cl12]2– dianion. Chem Commun 33:4991–4993
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M.N. acknowledges financial support by the Fonds der Chemischen Industrie.
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CCDC-1882464 ([PNP][HBr2]), 1882463 ([PNP]2[H6Cl4O2]), and 1882465 ([PNP]2[H6Br4O2]) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK). Further supplementary material (synthetic details, quantum-chemical calculations) is available in PDF format.
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Bertocco, P., Bolli, C., Correia Bicho, B.A. et al. Insights into the Structure of Halide-Rich Hydrochloric and Hydrobromic Acid: A Structural and Quantum-Chemical Investigation of the [H6X4O2]2− (X = Cl, Br) Anions. J Chem Crystallogr 50, 69–76 (2020). https://doi.org/10.1007/s10870-019-00773-w
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DOI: https://doi.org/10.1007/s10870-019-00773-w