Experimental and Theoretical Evidence of the Au(I) Bi(III) Closed-Shell Interaction

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1 Experimental and Theoretical Evidence of the Au(I) Bi(III) Closed-Shell Interaction Eduardo J. Fernández, a * Antonio Laguna, b * José M. López-de-Luzuriaga, a Miguel Monge, a M. Elena Olmos, a Mihai Nema, c Javier Pérez, a Cristian Silvestru c a Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC. Complejo Científico-Tecnológico, Logroño, SPAIN. b Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, Zaragoza, SPAIN. c Facultatea de Chimie si Inginerie Chimica, Universitatea Babes- Bolyai, RO Cluj-Napoca, Romania. ELECTRONIC SUPPLEMENTARY INFORMATION

2 Experimental Section. General. All reactions were carried out under dry deoxygenated argon atmosphere using Schlenk techniques. All solvents were distilled from an appropriate drying agent. [BiCl(C 6 H 4 CH 2 NMe 2-2) 2 ] 1 and [AuAg(C 6 F 5 ) 2 ] 0.5 OEt 2 2 were prepared according to literature methods. Instrumentation. Infrared spectra were recorded in the cm -1 range on a Perkin-Elmer FT-IR Spectrum 1000 spectrophotometer, using Nujol mulls between polyethylene sheets. Mass spectra were recorded on a HP-5989B Mass Spectrometer API-Electrospray with interface 59987A. 1 H, and 19 F NMR spectra were recorded on a Bruker Avance 400 in d 6 -acetone solutions. Chemical shifts are quoted relative to SiMe 4 ( 1 H external) and CFCl 3 ( 19 F external). Synthesis of [Au(C 6 F 5 ) 2 ][Bi(C 6 H 4 CH 2 NMe 2-2) 2 ] 1: To a dichloromethane solution (15 ml) of the diorganobismuth compound [BiCl(C 6 H 4 CH 2 NMe 2-2) 2 ] (0.100 g, mmol) was added [AuAg(C 6 F 5 ) 2 ] 0.5 OEt 2 (0.128 g, mmol). The reaction mixture was stirred for 2 h at room temperature and a white precipitate was formed. Filtration of the precipitate and evaporation of the solvent under vacuum and addition of diethyl ether gave rise to complex 1 as a white solid in 50% yield. Mass spectrum (ES-) m/z = 531 ([Au(C 6 F 5 ) 2 ] - ). 19 F NMR (282 MHz, d 6 -acetone), δ (m, 4F, F o ), (t, 2F, F p ), (m, 4F, F m ). 1 H NMR (400 MHz, d 6 -acetone), δ 8.27 (d, 2H, C 6 H 4 ), δ 7.76 (2, 2H, C 6 H 4 ), δ 7.62 (t, 2H, C 6 H 4 ), δ 7.42 (t, 2H, C 6 H 4 ), δ 4.39 (s, 4H, CH 2 -N), δ 2.91 (s, 12H, N(CH 3 ) 2 ). FT-IR (Nujol mulls): ν = 1500, 952, 790 cm -1 (Au-C 6 F 5 ).

3 Computational details. All calculations were performed using the Gaussian 03 suite of programs 3 using DFT/B3LYP, 4 Hartree-Fock and MP2 5 levels of theory The interaction energy between ionic counterparts at Hartree-Fock (HF) and MP2 levels of theory was obtained according to equation: Δ E = E ( AB) ( AB) ( AB) E E V ( R) AB A B = a counterpoise correction for the basis-set superposition error (BSSE) 6 on ΔE was thereby performed. We fitted the calculated points using a four-parameter equation, which had been previously used 7 to derive the Herschbach-Laurie relation: 8 Δ E = V ( R) = Ae BR CR n Table S1. Experimental and optimized theoretical distances (Å) and angles (deg) for model systems A, B and C. Au-Bi Au-C Bi-C Bi-N C-Au-C N-Bi-N C-Bi-Au Experim. X-Ray Model A (DFT) Model B (MP2, C s ) Model C (MP2, C s )

4 Basis Sets. The 19-valence electron (VE) quasirelativistic (QR) pseudopotential (PP) of Andrae 9 was employed for gold together with two f-type polarization functions (exponents: 0.2, 1.19). 10 The atoms Bi, F, N, and C were treated by Stuttgart pseudopotentials, 11 including only the valence electrons for each atom. For these atoms double-zeta basis sets of ref 11 were used, augmented by d-type polarization functions. 12 In the case of Bismuth we have augmented the basis sets as described in reference 13 in which several polarization functions were added. For the H atom, a double-zeta, plus a p-type polarization function was used. 14 (see Table S2) Table S2. Basis sets and Pseudopetentials used in the present work. Atom Pseudo potential Basis set Polarization function Au Andrae (ref. 9) (8s6p5d2f)/[6s5p3d2f) α f = 0.2, 1.19 Bi Dolg (ref 13) (6s6p3d3f)/[4s4p3d3f] α s = , α p = , α d = 0.27, 0.11, 0.04 α f = 0.50, 0.20, 0.08 C Bergner (ref 11) (4s4p1d)/[2s2p1d] α p = α d = 0.80 N Bergner (4s4p1d)/[2s2p1d] α p = α d = F Bergner (4s4p1d)/[2s2p1d] α p = α d = H - (4s1p)/[2s1p] α p = 0.8 References. [1] Carmalt, C. J.; Cowley, A. H.; Culp, R. D.; Jones, R. A.; Kamepalli, S.; Norman, N. C. Inorg. Chem. 1997, 36, 2770.

5 [2] Fernández, E. J.; Laguna, A.; López-de-Luzuriaga, J. M.; Monge, M. Spanish Patent P , [3] Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford CT, [4] a) Parr, R. G.; Yang, W. Density-functional theory of atoms and molecules; Oxford University Press: New York, b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. [5] a) Møller, C.; Plesset, M.S. Phys.Rev. 1934, 46, 618. b) Hehre, W.J.; Radom, L.; Schleyer, P.v.R.; Pople, J.A. Ab Initio Molecular Orbital Theory; John Wiley: New York, [6] Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553. [7] Pyykkö, P. Chem. Rev. 1997, 97, 597.

6 [8] Herschbach, D. R.; Laurie, V. W. J. Chem. Phys. 1961, 35, 458. [9] Andrae, D.; Häusserman, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor. Chim. Acta 1990, 77, 123. [10] Pyykkö, P.; Runeberg, N.; Mendizabal, F. Chem. Eur. J. 1997, 3, [11] Bergner, A.; Dolg, M.; Küchle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, [12] Huzinaga, S. Gaussian Basis Sets for Molecular Calculations; Elsevier: Amsterdam, 1984; p16. [13] a) Igel-Mann, G.; Dolg, M.; Stoll, H.; Preuss, H. Mol. Phys. 1988, 65, b) Küchle, W.; Dolg, M.; Stoll, H.; Preuss, H. Mol. Phys. 1991, 80, c) Klinkhammer, K. W.; Pyykkö, P. Inorg. Chem. 1995, 34, [14] Huzinaga S. J. Chem. Phys. 1965, 42, 1293.

7 OPTIMIZED GEOMETRIES IN XYZ FORMAT Fragment [Au(C 6 F 5 ) 2 ] - (D 2h symmetry) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Fragment [Bi(CH 3 ) 2 (NH 3 ) 2 ] (C 2v symmetry) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

8 Frangment [Bi(CH 3 ) 2 (NMe 2 H) 2 ] (C 2 symmetry) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Model A: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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