Dataset of polyoxometalate-assisted N-heterocyclic carbene gold(I) complexes

The present paper is the Supplemental materials for our original paper entitled “highly active, homogeneous catalysis by polyoxometalate-assisted N-heterocyclic carbene gold(I) complexes for hydration of diphenylacetylene. The present article refers to the preparations of several monomeric, N-heterocyclic (NHC) carbene/carboxylate (RS-pyrrld)/gold(I) complexes, [Au(RS-pyrrld)(NHC)] (NHC = IMes (6), BIPr (7), IF3 (8), ItBu (9)), which were used for homogenous catalysis of the hydration reaction of diphenylacetylene to afford deoxybenzoin. The article also includes the preparations of the precursor complexes, [AuCl(NHC)] (NHC = IPr, IMes, BIPr, IF3, ItBu), and novel X-ray crystallography of the separately prepared [Au(IPr)(H2O)]3[α-PW12O40]·7Et2O (2), summary of crystal data of (2), and selected bond distances (Å) and angles (deg) of (2). Also presented are Cartesian coordinates of the optimized structures in the quantum-mechanical calculations.


Data
Data presented in this article displays the preparations of several precursors used for homogenous catalysis of the hydration reaction of diphenylacetylene to afford deoxybenzoin; monomeric, N-heterocyclic (NHC) carbene/carboxylato/gold(I) complexes, [Au(RS-pyrrld)(NHC)] (NHC ¼ IMes (6), BIPr (7), IF 3 (8), I t Bu (9)), as well as the precursor complexes, [AuCl(NHC)] (NHC ¼ IPr, IMes, BIPr, IF 3 , I t Bu) [1]. Also presented are summary of crystal data of the separately prepared [Au(IPr)(H 2 O)] 3 [a-PW 12 O 40 ]$7Et 2 O (2) ( Table 1), selected bond distances (Å) and angles (deg) of (2) ( Table 2), and Cartesian coordinates of the optimized structures in the quantum-mechanical calculations ( Text files describing synthesis and tables How data was acquired NMR and single-crystal X-ray; The 1 H NMR (400 MHz), 31 P{ 1 H} NMR (161 MHz) and 13 C{ 1 H} NMR (99 MHz) spectra of the samples were recorded in 5-mm-outer-diameter tubes on a JEOL JNM-ECA 400 FT-NMR or a JEOL JNM-ECS-400 FT-NMR spectrometer and a JEOL ECA-400 NMR or ECS-400 NMR data processing system, respectively. Single crystals of the metal complex were mounted on a loop and used for measurements of cell constants and for the collection of intensity data on a Rigaku VariMax with Saturn CCD diffractometer. The structure was solved by a direct method, followed by difference Fourier calculation; it was refined by a full-matrix least-squares method on F 2 using the Yadokari program package. Value of the data The data in this article will be informative for researchers who work on the chemistry of gold-polyoxometalate hybrids. The data in this article will be useful for design of more active catalytic systems for alkyne hydration in the presence of polyoxometalates. Details of synthesis and characterization of N-heterocyclic carbene (NHC)-gold(I) complexes, [AuCl(NHC)], will be informative for synthesis of other related gold(I) complexes. The synthetic process of the catalytically active complexes, [Au(RS-pyrrld)(IPr)] (1) and [Au(RS-pyrrld)(NHC)] ((6)e(9)), using [AuCl(NHC)], will be applicable for other active gold(I) complexes. The data of X-ray molecular structure of [Au(IPr)(H 2 O)] 3 [a-PW 12 O 40 ] (2) as the actual catalyst precursor will be interesting for researchers on the chemistry of gold-polyoxometalate hybrids.

Experimental design, materials, and methods
CHN elemental analyses were carried out using a PerkinElmer 2400 CHNS Elemental Analyzer II (Kanagawa University). IR spectra were recorded on a Jasco 4100 FT-IR spectrometer in KBr disks at room temperature. TG/DTA was performed using a Rigaku Thermo Plus 2 series TG/DTA TG 8120 instrument.
The 1 H NMR (400 MHz), 31 P{ 1 H} NMR (161 MHz) and 13 C{ 1 H} NMR (99 MHz) spectra of the samples were recorded in 5-mm-outer-diameter tubes on a JEOL JNM-ECA 400 FT-NMR or a JEOL JNM-ECS-400 FT-NMR spectrometer and a JEOL ECA-400 NMR or ECS-400 NMR data processing system, respectively. The 1 H and 13 C{ 1 H} NMR spectra were referenced to an internal TMS. The 31 P{ 1 H} NMR spectra were

[AuCl(IPr)] [3]
To a solution of H [AuCl 4 ]$4H 2 O (1.00 g, 2.43 mmol) in 9 mL of 3-chloropyridine, HIPr þ Cl À [3] (1.03 g, 2.43 mmol) and then Na 2 CO 3 (1.03 g, 12.2 mmol) were sequentially added. The mixture was stirred for 24 h in an oil bath at ca 80 C, then cooled to room temperature, and 18 mL of CH 2 Cl 2 was added. The resulting brown suspension was filtered through a folded filter paper (Whatman #5). Dichloromethane was removed from the filtrate with a rotary evaporator at ca 30 C, and the residual solution was added to 300 mL of hexane, affording a yellow-white suspension. Filtration on a membrane filter (JV 0.1 mm) gave a yellow-white powder, which was washed with MeOH (10 mL x 2) and hexane (30 mL x 2), dried thoroughly by suction, and dried in vacuo for 2 h. Yield 0.366 g (24.3%). Anal

[AuCl(BIPr)] [5]
The complex [AuCl(BIPr)] was prepared by reaction of HBIPr þ Cl À [6] (0.291 g, 0.613 mmol) in 60 mL of acetone with [AuCl(THT)] [7,8] (0.271 g, 0.920 mmol) and K 2 CO 3 (0.424 g, 3.07 mmol) in an oil bath at ca 60 C for 2 h with stirring. The mixture was filtered through a membrane filter (JV 0.1 mm), and the filtrate was evaporated to dryness. The resulting pale purple solid was dissolved in 20 mL of CH 2 Cl 2 , and the solution was filtered through a folded filter paper (Whatman #5). The pale purple clear filtrate was added to 600 mL of hexane. Filtration on a membrane filter (JV 0.1 mm) gave a pale purple solid, which was washed with hexane (20 mL x 2), dried thoroughly by suction, and dried in vacuo for 2 h to afford a pale purple powder. Yield 0.1290 g (70.5%). Anal