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Dichlorophosphoranides Stabilized by Formamidinium Substituents

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Dichlorophosphoranides Stabilized by Formamidinium Substituents Hindawi Heteroatom Chemistry Volume 2020, Article ID 9856235, 6 pages https://doi.org/10.1155/2020/9856235 Research Article Dichlorophosphoranides Stabilized by Formamidinium Substituents Anatoliy Marchenko, Georgyi Koidan, Anastasiya Hurieva, Eduard Rusanov, Alexander B. Rozhenko, and Aleksandr Kostyuk Institute of Organic Chemistry National Academy of Sciences of Ukraine, Murmanska 5, 02660 Kyiv 94, Ukraine Correspondence should be addressed to Aleksandr Kostyuk; [email protected] Received 10 December 2019; Accepted 16 January 2020; Published 13 February 2020 Academic Editor: Mariateresa Giustiniano Copyright © 2020 Anatoliy Marchenko et al. (is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Dichlorophosphoranides featuring N,N-dimethyl-N′-arylformamidine substituents were isolated as individual compounds. Dichlorophosphoranide 9 was prepared by the multicomponent reaction of C-trimethylsilyl-N,N-dimethyl-N′-phenyl- formamidine and N,N-dimethyl-N′-phenylformamidine with phosphorus trichloride. Its molecular structure derived from a single-crystal X-ray diffraction was compared to the analogous dibromophosphoranide prepared previously by us by the reaction of phosphorus tribromide with N,N-dimethyl-N′-phenylformamidine. It was shown that a chlorophosphine featuring two N,N- dimethyl-N′-mesitylformamidine substituents reacted with hydrogen chloride to form dichlorophosphoranide 11. Its molecular structure was also determined by X-ray analysis and compared with that of closely related dichlorophosphoranide C. 1. Introduction publication, we have described the synthesis of dibromo- phosphoranide 3 by the reaction of N,N-dimethyl-N′-phe- Phosphoranides A are hypervalent anionic phosphorus(III) nylformamidine 1 with phosphorus tribromide in a 3 :1 compounds formally possessing a 10-electron valence shell ratio. Its structure was established by X-ray diffraction and a distorted pseudotrigonal bipyramidal arrangement at analysis. Based on DFT calculations, the mechanism for the phosphorus atom. (e electronegative ligands at formation of phosphoranide 3 has been suggested phosphines make nucleophilic addition possible to afford (Scheme 1) [6]. stable phosphoranides (Figure 1). (e final step of the proposed mechanism is the reaction (e first isolated phosphoranide has been prepared by of dibromophosphine 2 with N,N-dimethyl-N′-phenyl- the reaction of tetrapropylammonium bromide with formamidine. It should be noted that other P(III) halides, phosphorus tribromide, and its structure has been unam- such as phosphorus trichloride, dichlorophosphines, and biguously determined by a single-crystal X-ray diffraction monochlorophosphines, do not react with the for- study [1, 2]. Later, tetrachlorophosphoranides and tetra- mamidines. Earlier, we were unable to check the mechanism, fluorophosphoranides were prepared, with tetra- as dibromo(dichloro)phosphines featuring the formamidine fluorophosphoranide being the most stable derivative [3]. N- substituent were unavailable. Recently, we have developed a heterocyclic carbenes are known to be suitable for stabili- method for the synthesis of C-trimethylsilyl-N,N-dialkyl-N′- zation of high-coordinated P atoms. (e reaction of a ste- arylformamidines and studied their reactions with phos- rically hindered N-heterocyclic carbene with PCl3 in hexane phorus trichloride and chlorophosphines. A set of chlor- affords a high yield of phosphoranide B. (e imidazoliumyl ophosphines featuring two formamidine substituents were substituent efficiently stabilizes phosphoranides. Another isolated as stable compounds [7]. We assumed that example is phosphoranide C in which the imidazolium dichlorophosphines featuring the formamidine substituents moieties serve for stabilization [4, 5]. In our previous can be prepared by this method as well. It will allow 2 Heteroatom Chemistry Di X Dipp pp X N Cl Cl Di XP N pp P X P N Cl N Cl N Cl Dipp Dipp N Di TfO pp A B C Figure 1: Examples of phosphoranides stabilized by N-heterocyclic carbene ligands. ° ˚ 3 Ph Ph β � 106.412(1), c � 101.860(1) , V � 989.57(4) A , Z � 2, N N Ph − 1 PBr3 NMe2 dc � 1.33, μ 0.418 mm , F(000) 416, crystal size ca. Br N NMe P Br 2 0.33 × 0.47 × 0.54 mm. All crystallographic measurements Me N Br2P 2 1 Br Br were performed at 123K on a Bruker Smart Apex II dif- fractometer operating in the ω scans mode. (e intensity data were collected using Mo-Kα radiation (λ � 0.71078 A).˚ 1 PBr2 Br P 1,2-P shif (e intensities of 22667 reflections were collected (4183 2 Ph � N NMe2 N NMe unique reflections, Rmerg 0.033). Convergence for 9 was 1 ∗ HBr 2 Ph obtained at R1 � 0.0294 and wR � 0.058 for 3520 observed 2 reflections with I ≥ 3σ(I); GOF � 0.9332, R1 � 0.0360, and wR � 0.0617 for all 4167 data, 226 parameters, and the largest Ph and minimal peaks in the final difference map 0.34 and Ph H Br 3 N NMe N − ˚ 2 P 0.22 e/A . Br Crystal data for 11: (C H Cl N P ), M = 481.45, or- Me2N N 24 35 2 4 1 a Ph NMe thorhombic, space group Pna21, = 11.8655(3), 2 b = 14.1280(3), c = 15.3685(3) A,˚ V = 2576.31(10) A˚ 3, Z = 4, 3 − 1 dc = 1.241, μ 0.333 mm , F(000) 1024, crystal size ca. Scheme 1: Mechanism proposed for formation of dibromophos- 0.25 × 0.27 × 0.48 mm. All crystallographic measurements phoranide 3. were performed at 123K on a Bruker Smart Apex II dif- fractometer operating in the ω scans mode. (e intensities of investigation of the proposed mechanism and development 30253 reflections were collected (4944 unique reflections, of a method for the synthesis of phosphoranides. Rmerg = 0.039). Convergence for 11 was obtained at R1 = 0.0287 and wR = 0.0484, GOF = 0.9187 for 4259 ob- served reflections with I ≥ 3σ(I); GOF = 0.9187, R1 = 0.0363, 2. Materials and Methods and wR = 0.0525 for all 4923 data, 285 parameters, the largest All procedures with air- and moisture-sensitive compounds and minimal peaks in the final difference map 0.41 and ˚ 3 were performed under an atmosphere of dry argon in flame- − 0.31 e/A . (e structures were solved by direct methods dried glassware. Solvents were purified and dried by stan- and refined by the full-matrix least-squares technique in the dard methods. Melting points were determined with an anisotropic approximation for non-hydrogen atoms using electrothermal capillary melting point apparatus and were the SIR97 and Crystals program package [8, 9]. uncorrected. 1H spectra were recorded on a Bruker Avance 1,1-Bis(dimethylamino)-N,N-diisopropyl-N′-4-mesityl- DRX 500 (500.1 MHz) or Varian VXR-300 (299.9 MHz) phosphine-carboximidamide selenide (5a): To a frozen so- spectrometer. 13C NMR spectra were recorded on a Bruker lution of 4a (1.31 g, 5 mmol) in Et2O (15 mL), a solution of Avance DRX 500 (125.8 MHz) spectrometer. 31P NMR PCl3 (0.69 g, 5 mmol) in diethyl ether (15 mL) was added. spectra were recorded on a Varian VXR-300 (121.4 MHz) (e reaction mixture was allowed to warm to ambient ° spectrometer. Chemical shifts (δ) are reported in ppm temperature (15 C) with stirring. (e solvent was evapo- downfield relative to internal TMS (for 1H, 13C) and external rated. Benzene (5 mL) was added to the residue, and then, a 31 solution of dimethylamine (900 mg, 20 mmol) in benzene 85% H3PO4 (for P). Chromatography was performed on (6 mL) was added. (e mixture was stirred for 15 min, and silica gel Gerudan SI60. Elemental analyses were performed at the Microanalytical Laboratory of the Institute of Organic selenium (500 mg, 6 mmol) was added. (e resulting sus- ° Chemistry of the National Academy of Sciences of Ukraine. pension was stirred for 1 h at 15 C. (e insolubles were filtered off and washed with benzene (2 × 5 mL), and the filtrate was evaporated. (e residue was purified by silica gel 2.1. X-ray Structure Determination. Crystal data for 9: plate chromatography. Yield, 60%. Rf 0.2–0.45 ° 31 1 (C18H23Cl2N4P), M � 397.29, triclinic, space group P-1, (CH2Cl2–hexane 1 :1), m.p. 116–117 C; P{ H} NMR 1 a � 9.3377(2), b � 9.9530(2), c � 12.3654(3) A,˚ α � 108.414(1), (202 MHz, CDCl3): δ � 65.7 (JPSe � 793 Hz) ppm; H NMR Heteroatom Chemistry 3 ° ° 31 (300 MHz, CDCl3): δ � 2.10 (s, 6 H, CH3), 2.23 (s, 3 H, CH3), 0.05 Torr, m.p. 59–60 C (pentane, − 28 C); P NMR (81 MHz, 1 2.84 (d, J � 2.7 Hz), 2.87 (s, 18 H, NCH3), 6.77 (s, 2 H, CH) CDCl3): δ � 90.1 ppm; H NMR (500 MHz, C6D6): δ �1.34 (br 13 ppm; C NMR (125.7 MHz, C6D6): δ �18.6 (s, CH3), 20.2 (s, s, 12 H, CH3), 2.26 (s, 6 H, CH3), 2.27 (s, 3 H, CH3), 2.34 (d, CH3), 37.9 (s, CH3), 39.8 (s, CH3), 126.1 (s, ipso-C), 127.6 (s, J � 8.5 Hz, 12 H, NCH3), 3.93 (br s, 2 H, CH), 6.85 (s, 2 H, CH) 13 CH), 129.9 (s, ipso-C), 145.3 (d, J � 21 Hz, ipso-C), 150.5 (d, ppm; C NMR (125.7 MHz, C6D6): 19.1 (d, J � 4 Hz, CH3), 20.2 + J � 155 Hz, CN); EI-MS 387–100% [M + 2] ; elemental (s, CH3), 20.9 (s, CH3), 40.9 (d, J � 15 Hz, CH3), 47.8 (d, analysis calcd (%) for C16H29N4PSe (387.37) C 49.61, H 7.55, J � 13 Hz, CH), 124.1 (s, ipso-C), 126.0 (s, ipso-C), 127.9 (s, CH), N 14.46, P 8.00; found: C 49.84, H 7.37, N 14.62, P 8.26.
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