Phosphines featuring a hexafluorocyclopentene skeleton: Synthesis, coordination properties, and applications for Lewis-acidic transition-metal catalysts

Journal Pre-proof Phosphines featuring a hexafluorocyclopentene skeleton: Synthesis, coordination properties, and applications for Lewisacidic transition-metal catalysts

Tomohiro Agou, Nao Wada, Momoko Komatsu, Miki Nohara, Yoshiyuki Mizuhata, Norihiro Tokitoh, Takaaki Hosoya, Hiroki Fukumoto, Toshio Kubota PII:

S2211-7156(19)30008-6

DOI:

https://doi.org/10.1016/j.rechem.2019.100008

Reference:

RECHEM 100008

To appear in: Received date:

2 July 2019

Accepted date:

3 September 2019

Please cite this article as: T. Agou, N. Wada, M. Komatsu, et al., Phosphines featuring a hexafluorocyclopentene skeleton: Synthesis, coordination properties, and applications for Lewis-acidic transition-metal catalysts, (2019), https://doi.org/10.1016/ j.rechem.2019.100008

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© 2019 Published by Elsevier.

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Phosphines Featuring a Hexafluorocyclopentene Skeleton: Synthesis, Coordination Properties, and Applications for Lewis-Acidic Transition-Metal Catalysts

Tomohiro Agou,a,* Nao Wada,a Momoko Komatsu,a Miki Nohara,a Yoshiyuki Mizuhata,b

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Department of Quantum Beam Science, Graduate School of Science, Ibaraki University, 4-12-1

Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.

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b

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Nakanarusawa, Hitachi, Ibaraki 316-8511, Japan

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a

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Norihiro Tokitoh,b Takaaki Hosoya,a Hiroki Fukumotoa,* and Toshio Kubotaa,*

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* Corresponding authors at: Department of Quantum Beam Science, Graduate School of Science,

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Ibaraki University, 4-12-1 Nakanarusawa, Hitachi, Ibaraki 316-8511, Japan. E-mail addresses: [email protected] (T. Agou), [email protected] (H. Fukumoto), [email protected] (T. Kubota).

Keywords:

Fluorinated

phosphines,

Transition metal

Hydroarylation of alkynes, Hydration of alkynes

1

complexes,

Lewis

acid

catalysts,

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ABSTRACT Weakly -donating phosphines bearing a hexafluorocyclopentene skeleton were synthesized. The 1JPSe coupling constants of selenides of the fluorinated phosphines revealed substantially decreased s-character of the phosphorus lone pair orbitals of the fluorinated phosphines, indicating their weak -donating ability. Au(I), Pd(II) and Pt(II) complexes bearing the fluorinated phosphines

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showed moderate catalytic activity in the hydration and hydroarylation of alkynes.

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Graphical abstract

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1. Introduction Recently, much attention has been paid to weakly -donating and/or strongly -accepting ligands from the fields of both transition metal-complex chemistry and synthetic organic chemistry, because of their potential application to catalytic molecular transformation. Weakly -donating and strongly -accepting ligands can decrease the electron density of the transition metal centers and

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improve the Lewis acidity of the complexes, facilitating various transition metal-catalyzed reactions.

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For examples, trans-metalation and reductive elimination steps in cross coupling reactions are

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accelerated by weak -donor ligands, as shown by the rate enhancement of the Kosugi-Migita-Stille cross coupling reactions by (2-furyl)3P (Fig. 1) [1]. Incorporation of positive charges into phosphine

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frameworks remarkably accolated -Lewis acid-catalyzed reactions of alkynes [2-6]. Strongly

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-accepting phosphaalkene ligands have been applied to various molecular transformations catalyzed

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by -acidic transition metal complexes, because of the low lying *(P=C) orbitals working as acceptor orbitals [7-14].

Fig. 1. Representative P-ligands increasing the Lewis acidity of transition metals.

Poly-fluorinated phosphines such as P(C6F5)3 and (C6F5)2PCH2CH2P(C6F5)2 (“DPPE-F20”) 4

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(Fig. 2) are representative poor -donor ligands. Highly fluorinated phosphines show particular activity in various catalytic reactions: tandem activation of Si-H and C-H bonds [15,16], cycloisomerization of alkynes [17], addition of boronic acids to multiple bonds [18,19], hydroarylation of alkenes and alkynes [20-22], and hydration of alkynes [23]. Polyfluorinated phosphines can facilitate the reductive elimination of ArCF3, which is one of the most challenging

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reactions for transition metal catalysts [24]. Because of their potential application for transition metal

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been paid considerable attention to [25].

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catalysts, the development of poly-fluorinated phosphines with unique coordination properties have

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Fig. 2. Polyfluorinated phosphines.

Recently, we have been investigating the potential of a hexafluorocyclopentene skeleton as the key skeletons for -conjugated molecules [26,27], fluorinated polymers [28,29], and ligands [30]. Although the hexafluorocyclopentene-based phosphines 1b and 2b (Fig. 2) had appeared in literatures a half century ago [31,32], their applications for transition metal catalysts had not been described until our research began. d10 Coinage metal (Cu, Ag, and Au) complexes bearing 1b and 2b exhibited unique molecular structures and reactivity [30]. In particular, Au(I) complexes of 1b and 2b catalyzed the hydration of an alkyne without pre-activation using an Ag(I) co-catalyst, indicating that these fluorinated phosphines effectively improve the Lewis acidity of the Au(I) centers [11,13]. 5

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However, the catalytic activity of the neutral Au(I) complexes of 1b or 2b for the alkyne hydration remained moderate. In addition, application of the hexafluorocyclopentene-based phosphines for other catalytic reactions, such as hydroarylation of alkynes, have not been reported. Herein, we describe the synthesis

of new polyfluorinated phosphines

1a

and

2a

featuring the

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hexafluorocyclopentene framework and their application to catalysts.

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2. Results and discussion

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2.1. Synthesis of hexafluorocyclopentene-based phosphines

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p-CF3-C6H4 (ArF) groups were introduced on the P-centers of the new phosphines 1a and 2a in

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order to decrease the -donating ability. Phosphines 1a and 2a were synthesized following the

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synthetic methods for Ph-analogues 1b and 2b, respectively (Scheme 1) [30-32]. These phosphines

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were not oxidized even by treatment with aq. H2O2 at room temperature, suggesting their remarkably low -donor character. The reactions of 1 and 2 with elemental selenium afforded the phosphine selenides 3 and 4, respectively. Among the newly synthesized phosphines and phosphine selenides, 1a and 3b were structurally characterized by X-ray crystallography (Fig. 2). Their structures were closely related to those of the ordinary triarylphosphines and triarylphosphine selenides, respectively.

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Scheme 1. Syntheses of fluorinated phosphines 1 and 2 and phosphine selenides 3 and 4. a Ref. 30. b

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Estimated by 19F NMR spectroscopy.

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Fig. 3. Molecular structures of (a) phosphine 1a and (b) selenide 3b. Molecular structures of the

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compounds are shown below. Disordered fluorine atoms of the CF3 groups in 1a are omitted for clarity. Selected bond lengths (Å) and angles (deg): (a) P1-C1 1.830(4), P1-C2 1.828(3), P1-C3 1.829(2), P2-C4 1.824(4), P2-C5 1.835(3), P2-C6 1.823(2), C1-P1-C2 102.8(1), C1-P1-C3 103.3(1), C2-P1-C3 104.5(1), C4-P2-C5 103.5(2), C4-P2-C6 101.3(1), C5-P2-C6 100.1(2). (b) P1-Se1 2.0956(5), P1-C1 1.834(2), P1-C2 1.816(2), P1-C3 1.811(2), P2-C4 1.845(2), P2-C5 1.833(2), P2-C6 1.832(2), C1-P1-C3 104.71(9), C1-P1-C2 107.11(9), C2-P1-C3 106.5(1), Se1-P1-C1 108.43(7), Se1-P1-C2 112.96(7), Se1-P1-C3 116.48(7), C4-P2-C5 100.76(9), C4-P2-C6 102.10(9), C5-P2-C6 105.14(9).

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2.2. Evaluation of the s-character of the phosphorus lone pairs The s-character of the phosphorus lone pairs are related to the coordination properties of the phosphine ligands. The s-character can be assessed by the 1JPSe coupling constants of the corresponding phosphine selenides [1,33,34]. The 1JPSe coupling constants of the fluorinated phosphine selenides (3a: 818 Hz, 3b: 798 Hz, 4a: 808 Hz, 4b: 786 Hz) were increased relative to

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those of Ph3P=Se (732 Hz) [34] and were even larger than that of well-known poor -donor

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(2-furyl)3P (793 Hz) [33]. These data indicate the remarkably high s-character of the P-lone pairs in

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the fluorinated phosphines 1 and 2, which presumably suggests their poor basicity and -donor

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ability.

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2.3. Synthesis of transition metal complexes

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To investigate the coordination chemistry of 1 and 2, group 10 or 11 complexes of these fluorinated phosphines were synthesized (Scheme 2). Complexes 5b, 6b, and 9b have been described previously [30]. Complexes 5a, 8b and 9a were structurally characterized by X-ray crystallographic analysis (Fig. 3). Structure of iodide-bridged dinuclear Cu(I) complex 5a was closely related to the Ph-analogue 5b [30]. The UV/vis absorption spectrum of 5a (max 442 nm,  7.0×102) was similar to that of 5b (max 454 nm,  1.3×103) [30], suggesting that these complexes have comparable HOMO-LUMO energy gaps. DFT calculations indicated that the HOMO and LUMO of 5a (HOMO: –6.34 eV, LUMO: –3.19 eV) are stabilized relative to those of 5b (HOMO: –5.38 eV, LUMO: –2.32 8

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eV), whereas their HOMO-LUMO energy gaps and the energies of the S1 states are comparable (calcd 497 nm (f 0.0104) for 5a, 514 nm (f 0.0175) for 5b), in line with the UV/vis spectroscopic data. Geometric parameters around the metal centers of Pd complex 8b were similar to those of the related non-fluorinated phosphine complex [PdCl2{cis-(Ph2P)CH=CH(PPh2)}] [35]. Finally, the structure of

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9a was close to that of 9b [30].

Scheme 2. Synthesis of transition metal complexes 5-9 bearing fluorinated phosphines. a Ref. 30.

Fig. 4. Molecular structures of complexes 5a, 8b and 9a. Hydrogen atoms are omitted for clarity. For 9

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5a, disordered F atoms of the CF3 groups are not shown. For 8b, one of the two independent molecules is depicted here, and another molecule is shown in the supporting information. For 9a, disordered F and C atoms are omitted. Selected bond lengths (Å) and angles (deg): (a) Cu1-I1 2.6393(6), Cu1-I2 2.5867(6), Cu2-I1 2.5846(6), Cu2-I2 2.6229(6), Cu1-P1 2.314(1), Cu1-P2 2.300(1), Cu2-P3 2.307(1), Cu2-P4 2.292(1), Cu1-I1-Cu2 69.24(2), Cu1-I2-Cu2 69.02(2), I1-Cu1-I2

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109.09(2), I1-Cu2-I2 109.67(2), P1-Cu1-P2 87.19(4), P3-Cu2-P4 86.39(4); (b) Pd1-P1 2.218(2),

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Pd1-P2 2.222(3), Pd1-Cl1 2.347(3), Pd1-Cl2 2.349(2), P1-Pd1-P2 89.97(9), P1-Pd1-Cl1 85.92(9),

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P2-Pd1-Cl2 87.35(9), Cl1-Pd1-Cl2 96.74(9); (c) P1-Au1 2.227(1), Au1-Cl1 2.275(1), P1-Au1-Cl1

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171.05(4).

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2.4. Application for hydration of an alkyne

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The catalytic activity of the fluorinated phosphines was evaluated by the Ag(I)-free hydration of alkyne 10 (Table 2). Although there have been a plenty of reports on Au(I)- or Au(III)-catalyzed hydration of alkynes, the use of Ag(I) co-catalysts, which react with the Au(I) or Au(III) pre-catalyst complexes to generate catalytically active cationic Au complexes, is virtually inevitable [23, 36], except for few cases [37]. Ito et al. reported that Au(I) complexes bearing phosphaalkene ligands catalyzed the hydration of alkynes without pre-activation with Ag(I) co-catalysts [11,13]. We also found that neutral Au(I) complexes 6b and 9b exhibited moderate catalytic activity towards Ag(I)-free hydration of alkynes [30]. Such unusual reactivity of 6b and 9b may be explained in terms 10

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of the increased -Lewis acidity of the Au(I) centers by the poorly -donating phosphines 1b and 2b. Therefore, it was expected that Au(I) complexes 6a and 9a bearing the substantially weak -donors 1a and 2a, respectively, exhibited higher catalytic performances for the hydration of alkynes compared with 6b and 9b. As shown in Table 1, all the neutral Au(I) complexes catalyzed the hydration of alkyne 10 without Ag(I) co-catalysts. Unexpectedly, the dinuclear complexes 6a and 6b

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showed similar results (entries 1 and 2), indicating that the Ar F groups do not contribute to improve

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the catalytic activity in the case of dinuclear complexes. By contrast, an almost quantitative yield of

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11 was observed when the mononuclear complex 9a was used (entry 3). The Ph-analogue 9b showed

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much lower activity (entry 4). NMR analysis of the crude materials suggested that 6a completely decomposed to give a mixture of unidentified products during the catalytic reaction, whereas no

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improved catalytic activity.

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notable decomposition of 9a was observed. Such increased stability of 9a may be the reason for the

11

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Table 1. Au(I)-catalyzed hydration of alkyne 10.a

Au cat.

11 (%)

recovery of 10 (%)

1

6a (3 mol%)

58

42

2b

6b (3 mol%)

51

47

3

9a (6 mol%)

95

4b

9b (6 mol%)

35

61

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Yields were estimated by 1H NMR spectroscopy. b Ref. 30.

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entry

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Application for hydroarylation of alkynes.

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Fluorinated phosphine complexes 6-9 were applied to the hydroarylation of alkynes, a representative C-H activation/C-C bond forming reaction catalyzed by soft Lewis acidic complexes [2-5]. Alcarazo et al. reported that cationic phosphines, which are remarkably weak -donors, facilitated hydroarylation of alkynes, whereas typical cationic Au(I) catalysts (e.g., R3PAuCl + AgBF4, R = Ph, OPh) did not gave the arylation products [4]. Complexes 6-9 showed moderate catalytic activity towards the hydroarylation of phenylacetylene with mesitylene giving alkene 12 (R = Ph, R’ = H) (Table 2, entries 1-7). In general, the ArF-substituted complexes 6a (entry 1), 8a (entry 4), and 9a (entry 6) exhibited superior results as compared with the respective Ph-analogues 6b (entry 2), 8b (entry 5), and 9b (entry 7), suggesting the importance of the lower -donating ability of 12

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1a and 2a compared to those of 1b and 2b, respectively. By using the 9a + AgSbF6 catalyst system, diethyl acety-lenedicarboxylate (Table 5, entry 8) and 1-phenyl-1-propyne (entry 9) could be converted to the corresponding alkenes in moderate yields. In contrast, alkyl-substituted alkynes did not afford the corresponding hydroarylation products (entries 10 and 11), suggesting that electron-rich alkynes are not appropriate substrates for this catalyst. Furthermore, in all the cases, we

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did not observe the complete conversion of the alkynes to the corresponding hydroarylation products

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12 even with the most active catalyst 9a + AgSbF6, probably because of the limited lifetime of the

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catalytically active cationic species generated from the reaction of the Au(I) complexes and AgSbF6

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na

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[4]. Further optimization of the structures of the fluorinated phosphines is currently ongoing.

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Table 2. Hydroarylation of alkynes with mesitylene.a

R’

cat.

12 (%)

1

Ph

H

6ab

46

2

Ph

H

6bb

36

3

Ph

H

7

4

Ph

H

5

Ph

H

6

Ph

H

7

Ph

8

CO2Et

9

35

8a

38

8b

28

9a

54

9b

43

CO2Et

9a

38

Ph

Me

9a

60

10

n-C6H13

H

9a

0

11

Et

Et

9a

0

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R

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entry

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H

Yields were estimated by 1H NMR spectroscopy. b 6: 2.5 mol%.

3. Conclusion Hexafluorocyclopentene-based phosphines have been synthesized and shown to have poor -donating ability. Cu, Pd, and Pt complexes of the fluorinated phosphines were synthesized and 14

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structurally characterized. Au(I) complex of the fluorinated phosphines catalyzed the hydration of a terminal alkyne without pre-activation using Ag(I) salts, indicating that the fluorinated phosphines enhanced the Lewis acidity of the Au(I) center. In addition, Au(I), Pt(II), and Pd(II) complexes bearing the fluorinated phosphines exhibited moderate catalytic activity in the hydroarylation of alkynes. These results suggest the potential of fluorinated phosphines to develop new

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-acid-catalyzed reactions.

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4. Experimental

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4.1. General remarks

All the manipulations were performed under a dry N2 atmosphere using Schlenk techniques.

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Unless otherwise noted, materials obtained from commercial suppliers were used without further

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purifications. THF, Et2O and CH2Cl2 were purified by the Ultimate Solvent System, Glass Contour Company. Preparative gel permeation chromatography (GPC) was carried out by a Shimadzu Prominence HPLC system equipped with JAIGEL 1H+2H GPC columns. Preparative thin layer chromatography (PTLC) was performed using a homemade PTLC plate (Wakogel B-5F, 2 mm thickness). Column chromatography was performed using Kanto Silica Gel 60N (spherical, particle size 100-210 m). 1H,

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C,

19

F and

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P NMR spectra were measured on a Bruker Avance-III 400

spectrometer, and chemical shifts were reported as the delta scale in ppm relative to tetramethylsilane (1H and

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C), CFCl3 (19F), or 85% H3PO4 (31P). UV/vis spectra were recorded on a Shimadzu 15

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UV-3101PC spectrophotometer. High resolution mass spectra (HRMS) were recorded on a Bruker micrOTOF mass spectrometer (APCI, Internal standard: Tuning Mix), a JEOL JMS-700 MStation mass spectrometer (EI or FAB, Internal standard: PFK), or a Bruker solariX XR FT-MS system (ESI, APCI, or MALDI, Internal standard: CF3COONa). Elemental analysis was performed at the Instrumental Analysis Center, Ibaraki University, or at the Microanalytical Laboratory of the Institute

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for Chemical Research, Kyoto University.

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4.2. Synthesis of 1a

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To a Et2O (10 mL) solution of 1,2-dichlorohexafluorocyclopentene (0.30 mL, 2.0 mmol) was added n-BuLi (1.6 M in hexane, 1.4 mL, 2.4 mmol) at –75 °C, and the mixture was stirred for 30 min.

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To the mixture was added ClPArF2 (0.55 mL, 2.4 mmol). After stirring the mixture for 1 h, it was

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treated with s-BuLi (1.0 M in cyclohexane, 2.4 mL, 2.4 mmol) and stirred for 30 min. After addition of ClPArF2 (0.55 mL, 2.4 mmol), the mixture was stirred for 30 min and allowed to warm to room temperature. After stirring for 1 h, the mixture was treated with saturated aq. NH4Cl, and the aqueous layer was extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The residue was recrystallized from CH 2Cl2 to afford 1a as colorless crystals (0.65 g, 1.2 mmol, 60%). 1H NMR (400 MHz, CDCl3):  = 7.53 (d, 8H, J = 8.3 Hz), 7.39 (m, 8H); 13C{1H} NMR (100 MHz, CDCl3):  = 134.7 (d, J = 28.9 Hz), 134.5 (d, J = 22.9 Hz), 132.5 (d, J = 32.9 Hz), 125.6 (d, J = 3.7 Hz), 123.5 (q, J = 272.3 Hz). 13C NMR signals 16

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attributable to the hexafluorocyclopentene moiety could not be observed;

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F NMR (376 MHz,

CDCl3):  = –63.2 (s, 12F), –105.3 (m, 4F), –132.5 (m, 2F); 31P{1H} NMR (128 MHz, CDCl3):  = – 22.7 (s); HRMS (ESI+) m/z calcd for C33H16F18P2 816.0434. Found: 816.0433 (M+).

4.3. Synthesis of 2a

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To a Et2O (10 mL) solution of 1,2-dichlorohexafluorocyclopentene (0.3 mL, 2.0 mmol) was

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added n-BuLi (1.6 M in hexane, 1.4 mL, 2.4 mmol) at –75 °C, and the mixture was stirred for 30 min.

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To the mixture was added ClPArF2 (0.55 mL, 2.4 mmol). After stirring the mixture for 1 h, the

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mixture was allowed to warm to room temperature. After stirring for 3 h, the mixture was treated with saturated aq. NH4Cl, and the aqueous layer was extract-ed with CH2Cl2. The combined organic

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layer was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The

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residue was separated by using a GPC to afford 2a as a yellow solid (0.54 g, 0.66 mmol, 33%). 1H NMR (400 MHz, CDCl3):  = 7.69 (d, 4H, J = 8.4Hz), 7.55 (t, 4H, J = 8.4 Hz); 13C{1H} NMR (100 MHz, CDCl3):  = 134.5 (d, J = 22.7 Hz), 133.8 (d, J = 10.4 Hz), 132.9 (q, J = 33.0 Hz), 125.8 (m), 123.5 (q, J = 272.6 Hz ).

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C NMR signals attributable to the CF2 carbon atoms of the

hexafluorocyclopentene moiety could not be observed; 6F), –104.2.(m, 2F), –114.3 (m, 2F), –130.3(m, 2F);

31

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F NMR (376 MHz, CDCl3):  = –63.2 (s,

P{1H} NMR (128 MHz, CDCl3):  = –22.6

(s); HRMS (ESI+) m/z calcd for C19H9ClF12P: 530.9934. Found: 530.9933 ([M+H]+).

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4.4. Synthesis of the selenides. Representative procedure. To a toluene (20 mL) solution of 1a (41 mg, 0.050 mmol) was added elemental selenium (40 mg, 0.50 mmol), and the mixture was refluxed for 1 day. Remaining selenium was filtered off, and the filtrate was concentrated to afford selenide 3a (37 mg, 0.042 mmol, 84%). 1H NMR (400 MHz, CDCl3): δ = 8.03-8.09 (m, 4H), 7.79 (m, 4H), 7.57 (d, J = 7.7 Hz, 4H), 7.24-7.28 (m, 4H); 13C{1H}

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NMR (100 MHz, CDCl3):  = 133.9 (qd, J = 30.4, 3.2 Hz), 133.4 (d, J = 12.9 Hz), 133.3 (d, J = 21.3

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Hz), 132.5 (d, J = 12.5 Hz), 131.4 (q, J = 32.7 Hz), 130.7 (d, J = 78.6 Hz), 124.7 (m), 124.4 (m), 13

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122.6 (q, J = 272.5 Hz), 122.2 (q, J = 274.2 Hz). 19

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hexafluorocyclopentene moiety could not be observed;

C NMR signals attributable to the

F NMR (376 MHz, CDCl3):  = –63.2 (s,

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6F), –63.3 (s, 6F), –105.3 (s, 2F), –106.4 (s, 2F), –132.9 (s, 2F); 31P{1H} NMR (128 MHz, CDCl3): 

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= 19.3 (d, J = 22.8 Hz, 1JPSe = 818Hz), –26.9 (d, J = 22.8 Hz); HRMS (EI+) m/z calcd for

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C33H16F18P280Se: 895.9607. Found: 895.9604 (M+); calcd for C33H16F18P278Se: 893.9621. Found: 893.9604 (M+); calcd for C33H16F18P282Se: 897.9624. Found: 897.9612 (M+).

4.5. Selenide 3b

Following the representative procedure, reaction of 1b (27 mg, 0.050 mmol) and selenium (40 mg, 0.50 mmol) in refluxing CHCl3 afforded an inseparable mixture 3b and bisselenide 13 (molar ratio 92:8) indicated by the 19F and 31P NMR spectroscopy. The yield of 3b was estimated as 52% on the basis of the

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F NMR spectroscopy. 3b: 1H NMR (400 MHz, CDCl3):  = 7.92-7.98 (m, 4H), 18

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7.55-7.60 (m, 2H), 7.47-7.51 (m, 4H), 7.33-7.37 (m, 2H), 7.27-7.31 (m, 4H), 7.18-7.22 (m, 4H); C{1H} NMR (100 MHz, CDCl3):  = 134.0 (d, J = 21.4 Hz), 133.1 (d, J = 11.1 Hz), 132.4 (d, J =

13

2.8 Hz), 130.8 (d, J = 11.0 Hz), 129.5 (s), 128.6 (d, J = 13.2 Hz), 128.4 (d, J = 80.2 Hz), 128.3 (d, J = 7.3 Hz);

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F NMR (376 MHz, CDCl3):  = –105.9 (s, 2F), –107.0 (s, 2F), –133.3 (m, 2F);

31

P{1H}

NMR (128 MHz, CDCl3):  = 21.1 (d, J = 23.3 Hz, 1JPSe = 798 Hz), –25.2 (brs); HRMS (EI+) m/z

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calcd for C29H20F6P280Se: 624.0112. Found: 624.0109 (M+); calcd for C29H20F6P278Se: 622.0124.

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Found: 622.0128 (M+); calcd for C29H20F6P282Se: 626.0126. Found: 626.0121 (M+). 16:

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F NMR

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4.6. Selenide 4a

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(s). 77Se satellite signals could not be observed.

-p

(376 MHz, CDCl3):  = –104.4 (s, 4F), –135.1 (m, 2F); 31P{1H} NMR (128 MHz, CDCl3):  = 22.7

Following the representative procedure, reaction of 2a (27 mg, 0.050 mmol) and selenium (40 mg, 0.50 mmol) in refluxing toluene afforded 4a (17 mg, 0.028 mmol, 56%). 1H NMR (400 MHz, CDCl3):  = 8.00-8.06 (m, 4H), 7.81-7.83 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3):  = 134.1 (qd, J = 32.2, 3.1 Hz), 132.1 (d, J = 12.6 Hz), 129.6 (d, J = 79.1 Hz), 125.0 (m), 122.1 (q, J = 273.0 Hz). 13

C NMR signals attributable to the hexafluorocyclopentene moiety could not be observed; 19F NMR

(376 MHz, CDCl3):  = –63.4 (m, 6F), –103.7 (s, 2F), –114.6 (s, 2F), –130.5 (s, 2F); 31P{1H} NMR (128 MHz, CDCl3):  = 17.5 (s, 1JPSe = 808 Hz); HRMS (FAB+) m/z calcd for C19H8ClF12P80Se: 19

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609.9024. Found:

609.9016 (M+); C19H8ClF12P78Se:

607.9037. Found:

607.9030 (M+);

C19H8ClF12P82Se: 611.9012. Found: 609.9005 (M+).

4.7. Selenide 4b

of

Following the representative procedure, reaction of 2b (20 mg, 0.050 mmol) and selenium

ro

(40 mg, 0.50 mmol) in refluxing CHCl3 afforded 4b (19 mg, 0.040 mmol, 80%). 1H NMR (400 MHz,

-p

CDCl3):  = 7.87-7.93 (m, 4H), 7.58-7.62 (m, 2H), 7.51-7.56 (m, 4H);

13

C{1H} NMR (100 MHz,

lP

re

CDCl3):  = 132.9 (d, J = 3.3 Hz), 132.7 (d, J = 11.9 Hz), 129.0 (d, J = 13.4 Hz), 126.7 (d, J = 80.6 Hz ). 13C NMR signals attributable to the hexafluorocyclopentene moiety could not be observed; 19F

na

NMR (376 MHz, CDCl3):  = –104.2 (m, 2F), –114.6 (m, 2F), –130.6 (m, 2F); 31P{1H} NMR (128

Jo ur

MHz, CDCl3):  = 19.7 (s, 1JPSe = 786 Hz); HRMS (FAB+) m/z calcd for C17H10ClF6P80Se: 473.9276. Found: 473.9280 (M+); calcd for C17H10ClF6P78Se: 471.9288. Found: 471.9293 (M+); calcd for C17H10ClF6P82Se: 475.9263. Found: 475.9267 (M+).

4.8. Cu complex 5a To a slurry of CuI (7.1 mg, 0.037 mmol) in CH2Cl2 (3 mL) was added 1a (31 mg, 0.037 mmol), and the resulting solution was stirred for 1 d in the absence of light. The mixture was treated with

20

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saturated aq. NH4Cl, and the aqueous layer was extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The residue was recrystallized from CH2Cl2 and acetone to afford 5a as red crystals (42 mg, 0.031 mmol, 84%). 1

H NMR (400 MHz, CDCl3):  = 7.45-7.54 (m, 32H);

24F), –106.1 (m, 8F), –131.7 (m, 4F);

31

19

F NMR (376 MHz, CDCl3):  = –63.6 (s,

P{1H} NMR (128 MHz, CDCl3):  = –29.8 (brs); UV/vis

of

(CH2Cl2): max 442 nm ( 7.0×102). Anal. calcd for C66H32Cu2F36I2P4•acetone: C, 40.00; H, 1.85.

lP

4.9. Pt complex 7

re

-p

ro

Found: C, 40.12; H, 2.08.

na

To a solution of K2PtCl4 (75 mg, 0.18 mmol) in H2O (6 mL) was added a solution of 1b (0.10

Jo ur

g, 0.18 mmol) in THF (5 mL), and the resulting solution was stirred for 1 d. The mixture was treated with saturated aq. NH4Cl, and the aqueous layer was extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The residue was washed with Et2O and dried in vacuo to afford 7 as colorless crystals (45 mg, 56 μmol, 31%). 1H NMR (400 MHz, CDCl3):  = 7.83-7.89 (m, 8H), 7.63-7.67 (m, 4H), 7.54-7.59 (m, 8H); 19

F NMR (376 MHz, CDCl3):  = –108.2 (s, 4F), –129.2 (m, 2F); 31P{1H} NMR (128 MHz, CDCl3):

 = 35.0 (s, 1JPPt = 1842 Hz). Anal. calcd for C29H20Cl2F6P2Pt•Et2O: C, 43.27; H, 3.51. Found: C, 43.57; H, 3.19. 21

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4.10. Pd complex 8a

To a solution of Na2PdCl4 (36 mg, 0.12 mmol) in MeOH (8 mL) was added 1a (0.10 g, 0.12 mmol), and the resulting solution was stirred for 1 d. The mixture was treated with saturated aq.

of

NH4Cl, and the aqueous layer was extracted with CH2Cl2. The combined organic layer was dried

ro

over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The residue was

-p

recrystallized from CH2Cl2 to afford 8a as yellow crystals (0.11 g, 0.11 mmol, 92%). 1H NMR (400

31

P{1H} NMR (128 MHz, CDCl3):  = 53.6 (s). Anal.

lP

63.6 (s, 12F), –107.5 (s, 4F), –128.4 (s, 2F);

re

MHz, CDCl3):  = 7.96-8.02 (m, 8H), 7.88 (d, J = 7.1 Hz, 8H); 19F NMR (376 MHz, CDCl3):  = –

4.11. Pd complex 8b

Jo ur

na

calcd for C33H16Cl2F18P2Pd: C, 39.89; H, 1.62. Found: C, 40.01; H, 2.02.

To a solution of Na2PdCl4 (54 mg, 0.18 mmol) in MeOH (7 mL) was added 1b (0.10 g, 0.18 mmol), and the resulting solution was stirred for 1 d. The mixture was treated with saturated aq. NH4Cl, and the aqueous layer was extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The residue was recrystallized from CH2Cl2 to afford 8b as yellow crystals (0.13 g, 0.18 mmol, 100%). 1H NMR (400

22

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MHz, CDCl3):  = 7.85-7.90 (m, 8H), 7.65-7.69 (m, 4H), 7.54-7.59 (m, 8H); CDCl3):  = –108.2 (s, 4F), –129.0 (m, 2F);

31

19

F NMR (376 MHz,

P{1H} NMR (128 MHz, CDCl3):  = 55.6 (s). Anal.

calcd for C29H20Cl2F6P2Pd: C, 48.26; H, 2.79. Found: C, 47.99; H, 2.89.

of

4.12. Au complex 6a

-p

ro

To a solution of [AuCl(tetrahydrothiophene)] (64 mg, 0.20 mmol) in CH2Cl2 (5 mL) was

re

added 1a (82 mg, 0.10 mmol), and the resulting solution was stirred for 1 d. The solution was filtered and evaporated. The residue was recrystallized from CH2Cl2 and acetone to afford 6a as yellow

19

F NMR (376 MHz, CDCl3):  = –63.6 (s, 12F), –103.9 (s, 4F), –132.1 (m, 2F); 31P{1H}

na

(m, 8H);

lP

crystals (108 mg, 0.085 mmol, 85%). 1H NMR (400 MHz, CDCl3):  = 7.75-7.77 (m, 8H), 7.67-7.72

Jo ur

NMR (128 MHz, CDCl3):  = 14.7 (brs). Anal. calcd for C33H16Au2Cl2F18P2•0.5acetone: C, 31.63; H, 1.46. Found: C, 31.77; H, 1.46.

4.13. Au complex 9a

To a solution of [AuCl(tetrahydrothiophene)] (32 mg, 0.10 mmol) in CH2Cl2 (5 mL) was added 2a (53 mg, 0.10 mmol), and the resulting solution was stirred for 1 d. The solution was filtered and evaporated. The residue was recrystallized from CH2Cl2 to afford 9a as colorless crystals (73 mg, 23

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0.095 mmol, 95%). 1H NMR (400 MHz, CDCl3):  = 7.80-7.87 (m, 8H);

19

F NMR (376 MHz,

CDCl3):  = –63.5 (s, 6F), –103.0 (s, 2F), –114.1 (m, 2F), –129.9 (m, 2F); 31P{1H} NMR (128 MHz, CDCl3):  = 15.2 (s). Anal. calcd for C19H8AuClF12P: C, 29.91; H, 1.06. Found: C, 29.67; H, 1.34.

of

4.14. X-Ray crystallographic analysis

-p

ro

Single crystals of 1a, 3b, 5a, 8b and 9a suitable for X-ray diffraction analysis were obtained by re-crystallization from CH2Cl2-MeOH. X-Ray diffraction data were recorded on a Rigaku Saturn

lP

re

724+ diffractometer equipped with a VariMax Mo optic system using Mo-K radiation ( = 0.71075 Å) at 173 K. The reflection data were integrated, scaled and averaged by using the CrysAlisPro (ver.

na

1.171.38.46, Rigaku Oxford Diffraction, 2015). Empirical absorption corrections were applied using

Jo ur

the SCALE3 ABSPACK scaling algorithm (CrysAlisPro). The structures were solved by a direct method (SHELXT-2014/5) and refined by full-matrix least square method on F2 for all reflections (SHELXL-2014/7) [38]. All hydrogen atoms were placed using AFIX instructions, while all the other atoms were refined anisotropically. Selected crystallographic data are summarized in Table 3.

24

Journal Pre-proof Table 3. Crystallographic data for 1a, 3b, 5a, 8b and 9a. 3b

5a

8b

9a

formula

C33H16F18P2

C29H20F6P2Se

C66H32Cu2F36P4I2

C29H20Cl2F6P2Pd

C19H8AuCl2F12P

FW

816.40

623.35

2013.67

711.61

763.09

crystal system

monoclinic

triclinic

monoclinic

orthorhombic

monoclinic

space group

C2/c

P-1

P21/n

P212121

C2/c

crystal size (mm)

0.12×0.11×0.06

0.13×0.06×0.05

0.11×0.09×0.08

0.13×0.12×0.08

0.18×0.15×0.15

color

colorless

orange

orange

yellow

colorless

crystal description

platelet

block

block

block

block

a (Å)

30.967(3)

9.6604(3)

12.3976(7)

b (Å)

11.2185(5)

10.2533(3)

c (Å)

24.264(3)

 (deg)

22.798(1)

23.5214(7)

15.9723(6)

10.7681(1)

13.8755(4)

24.7447(8)

35.362(1)

18.5332(8)

90

74.826(3)

90

90

90

 (deg)

128.92(2)

83.993(2)

91.4388(3)

90

90.661(4)

 (deg)

90

87.192(2)

90

90

90

V (Å3)

6559(2)

1318.85(7)

7213.5(5)

5732.3(3)

4549.4(4)

Dcalcd (g cm-3)

1.654

1.570

1.854

1.649

2.228

Z

8

2

4

8

8

Independent

6096 (0.0569)

4868 (0.0288)

13411 (0.0616)

10602 (0.0655)

4210 (0.0306)

re

lP

na

Jo ur

reflections (Rint)

ro

10.1491(1)

-p

of

1a

R1 (I>2(I))

0.0546

0.0316

0.0411

0.0560

0.0236

wR2 (all data)

0.1544

0.0806

0.1043

0.1198

0.0603

GOF on F2

1.013

1.062

1.070

1.016

1.030

0.599, –0.461

0.363, –256

1.004, –0.461

1.120, –0.545

1.111, –1.001

Largest diff. peak and hole (e Å ) -3

4.15. Theoretical calculations

Molecular structures were optimized at the CAM-B3LYP/6-31G(d) (SDD for Cu and I) level 25

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of theory. Frequency calculations confirmed that the optimized structures corresponded to the energy equilibrium structures. TD-DFT calculations for complex 5a were carried out at the CAM-B3LYP/6-31+G(d) (SDD for Cu, I) level. DFT calculations were performed using the

of

Gaussian 16 (rev. B.01) program package [39].

ro

4.16. Catalytic hydration of alkyne 10. Representative procedure

re

-p

To a solution of 9a (11 mg, 15 μmol) in 1,4-dioxane (1.9 mL) and H2O (0.63 mL) was added

lP

acetate 10 (43 mg, 0.25 mmol) [36]. After stirring at 25 °C for 24 h, the solvent was removed under reduced pressure, and the crude material was analyzed by 1H NMR spectroscopy, showing that

na

2-oxo-1-phenylpropyl acetate (11) was generated in 95% yield. Spectral data were identical to those

internal standard.

Jo ur

previously reported [36]. Yields were estimated by 1H NMR spectroscopy using anisole as an

4.17. Hydroarylation of alkynes. Representative procedure

To 9a (9.5 mg, 12.5 μmol) was added AgSbF6 (5.8 mM in ClCH2CH2Cl, 2.5 mL, 14.5 μmol), and the mixture was stirred for 5 min at room temperature. To the mixture was added diethyl acetylenedicarboxylate (40 μL, 0.25 mmol) and mesitylene (0.14 mL, 1.0 mmol), and the mixture 26

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was stirred at 60 °C for 1 h. The solvent was removed under reduced pressure, and the crude material was analyzed by 1H NMR spectroscopy, showing the generation of alkene 12 (R = R’ = COOEt) in 38% yield, judging from the 1H NMR spectrum using anisole as an internal standard. The crude material was separated by GPC to afford the alkene as a yellow liquid (25 mg, 86 μmol, 34%). Its NOESY spectrum did not exhibited the noticeable nOe correlations between the H-C=C proton and

of

the methyl and aryl protons of the Mes group, indicating the (E)-configuration. 1H NMR (400 MHz,

ro

CDCl3):  = 7.11 (s, 1H), 6.86 (s, 2H), 4.25 (q, J = 7.2 Hz, 2H), 4.03 (q, 2H, J = 7.2 Hz, 2H), 2.23 (s,

-p

3H), 2.09 (s, 6H), 1.26 (t, J = 7.2 Hz, 3H), 1.05 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):  =

lP

re

166.1, 164.9, 144.4, 137.2, 135.1, 131.0, 129.9, 127.8, 61.7, 60.6, 21.1, 19.9, 14.1, 13.7. HRMS (EI+)

Jo ur

Conflict of interests

na

m/z calcd for C17H22O4 290.1518. Found: 290.1517 (M+).

There are no conflicts of interests.

Acknowledgements The work was supported by JSPS KAKENHI (Grant Nos. JP15H05477, JP15K05513 and JP16K1953), the Ibaraki University Priority Research Grant, and Shorai Foundation for Science and Technology. Computational time was provided by the Supercomputer Laboratory, Institute for Chemical Re-search, Kyoto University. HRMS measurements were support-ed by ICR-JURC, Kyoto 27

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University (Grant Nos. 2017-97 and 2018-105).

Appendix A. Supplementary data Supplementary material related to this article can be found in the online version, at DOI:#.

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Vila,

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[36] N. Ghosh, S. Nayak, A.K. Sahoo, Gold-Catalyzed Regioselective Hydration of Propargyl Acetates Assisted by a Neighboring Carbonyl Group: Access to -Acyloxy Methyl Ketones and Synthesis of (±)-Actinopolymorphol, J. Org. Chem. 76 (2011) 500-511. [37] J. Oliver-Meseguer, J.R. Cabrero-Antonino, I. Domínguez, A. Leyva-Pérez, A. Corma, Small Gold Clusters Formed in Solution Give Reaction Turnovers of 107 at Room Temperature, Science 338 (2012) 1452−1455. [38] G.M. Sheldrick, Crystal structure refinement with SHELXL. Acta Cryst. C71 (2015) 3-8. [39] M.J. Frisch, et al. Gaussian 16, Revision B.01, Gaussian Inc., Walling-ford, CT, 2016. Complete 33

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Highlights 

New polyfluorinated phosphines featuring a hexafluorocyclopentene framework were synthesized.

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The polyfluorinated phosphines exhibited remarkably decreased -donating ability.

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Au(I) complexes of the polyfluorinated phosphines catalyzed the hydration and

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hydroarylation of alkynes.

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