Phenyl Exchange Reaction within Vinyl Nickel Complexes

Article Cite This: Organometallics XXXX, XXX, XXX-XXX

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Vinyl/Phenyl Exchange Reaction within Vinyl Nickel Complexes Bearing Chelate [P, S]-Ligands Benjing Xue,† Hongjian Sun,† Shishuai Ren,† Xiaoyan Li,*,† and Olaf Fuhr‡ †

School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250199 Jinan, P. R. China ‡ Institut für Nanotechnologie (INT) und Karlsruher Nano-Micro-Facility (KNMF), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany S Supporting Information *

ABSTRACT: Three nickel(II) hydrides, [2-Ph2P(4-Me-C6H3)S]NiH(PMe3)2 (1), [2-Ph2P(6-Me3Si-C6H3)S]NiH(PMe3)2 (2), and [2-Ph2P(4-Me3Si -C6H3)S]NiH(PMe3)2 (3), were synthesized via S−H bond activation through the reaction of Ni(PMe3)4 with (2-diphenylphosphanyl)thiophenols. The reactions of nickel(II) hydrides (1−3) with different alkynes were investigated. Although the first step is the insertion of alkyne into the Ni−H bond for each reaction, different final products were isolated. Normal vinyl nickel complex [2-Ph2P(4Me-C6H3)S]Ni(CPhCH2)(PMe3) (4) was obtained by the reaction of phenylacetylene with 1. The nickelacyclopropane complexes [2-Ph2P(6-Me3SiC6H3)S]Ni[Ph(PMe3)C−CH2] (5), [2-Ph2P(4-Me3Si-C6H3)S]Ni[Ph(PMe3)C−CH2] (6), [2-Ph2P(4-Me3-C6H3)S]Ni[Ph(PMe3)C−CHPh] (7), [2-Ph2P(6-Me3Si-C6H3)S]Ni[Ph(PMe3)C−CHPh] (8), [2-Ph2P(4-Me3Si-C6H3)S]Ni[Ph(PMe3)C−CHPh] (9), [2-Ph2P(4-Me-C6H3)S]Ni[Ph(PMe3)C−CHSiMe3] (10) or [2-Ph2P(4-Me-C6H3)S]Ni[Me3Si(PMe3)C−CHPh] (10), [2-Ph2P(6-Me3Si-C6H3)S]Ni[Ph(PMe3)C−CHSiMe3] (11) or [2-Ph2P(6-Me3Si-C6H3)S]Ni[Me3Si(PMe3)C−CHPh] (11), and [2-Ph2P(4-Me3Si-C6H3)S]Ni[Ph(PMe3)C−CHSiMe3] (12) or [2-Ph2P(4-Me3Si-C6H3)S]Ni[Me3Si(PMe3)C−CHPh] (12) containing a ylidic ligand were formed by the reaction of phenylacetylene, diphenylacetylene, and 1-phenyl-2-(trimethylsilyl)acetylene with 1, 2, and 3, respectively. The phenyl/vinyl exchange nickel(II) complexes [2-(Ph(CH2CSiMe3)P(4-Me-C6H3)S]Ni(Ph)(PMe3) (13), [2-(Ph(CH2CSiMe3)P((6Me3Si-C6H3)S]Ni(Ph)(PMe3) (14), and [2-(Ph(CH2CSiMe3)P((4-Me3Si-C6H3)S]Ni(Ph)(PMe3) (15) could be obtained by insertion of trimethylsilylacetylene into Ni−H bonds of 1, 2, and 3. To the best of our knowledge, this is a novel reaction type between alkyne and nickel hydride. The results indicate that whether increasing the electronegativity on the benzene ring or on the alkyne leads to the instability of the vinyl nickel complex, and is beneficial to the C−P reductive elimination to form nickelacyclopropane complexes or phenyl nickel complexes via vinyl/phenyl exchange reaction in the case of the more electronegative nickel center. All the nickel complexes were fully detected by IR, NMR and the molecular structures of complexes 1, 2, 7, 9, 13, and 14 were confirmed by single crystal X-ray diffraction.

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INTRODUCTION The insertion of alkynes into an M−H bond is one of the essential methods in formation of metal alkenyl complexes.1 The first step of alkyne insertion into an M−H bond is the coordination of the alkynes to the metal center, confirmed by experimental and mechanistic studies.2 In recent years, the metals involved in insertion reaction of alkynes are Ir,3 Os,4 Pt,5 and Ru.6 In 2002, Yamaguchi has reported the reactions of a dmpm and dihydrido-bridged diiridium complex with alkynes to give μ-vinyl complexes.3a Puddephatt has reported the reversible insertion of alkynes into [Ru2(μ-H)(μ-CO)(CO)4(μdppm)2]+ to give [Ru2(μ-CHCH2)(CO)4(μ-dppm)2]+ and [Ru2(μ-CHCHPh)(CO)4(μ-dppm)2]+.6b Although hydrido nickel complexes have been synthesized and utilized among many reactions,7 few examples of vinyl nickel and nickelacyclopropane complexes have been reported via the insertion reaction of Ni−H bonds by alkynes. Furthermore, as a special © XXXX American Chemical Society

class of compounds, metalacyclopropanes are known as key intermediates in olefin polymerization.8 Carmona’s group reported the insertion reactions of phenylacetylene into the Ni−COR bond of the corresponding NiCl(COR)(PMe3)2 derivatives. A nickelacyclopropane complex could be obtained by an isomeric rearrangement of vinyl nickel complex.9 In 2005, Vicic studied the electrochemistry of the 1-norbornene complex and suggested a nickelacyclopropane extreme of olefin binding, stemming from the highly reactive nature of the bridgehead double bond.10 Normally, reductive elimination is the combination of two anionic ligands at one metal center to provide an organic molecule with the decrease (−2) of the metal oxidation state. In some cases, the anionic carbon and the neutral phosphorus Received: September 5, 2017

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DOI: 10.1021/acs.organomet.7b00671 Organometallics XXXX, XXX, XXX−XXX

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Organometallics atom could also be linked via reductive elimination.11 The vinyl palladium complex trans-[Pd(CHCHPh)Br(PhMePh2)2] underwent the reductive elimination between Pd−C and Pd− P bonds to furnish the corresponding phosphonium Pd(0) complex. Alkyl phosphonium salts could also be formed via C− P reductive elimination catalyzed by Pd complex.12 In our previous work, the reactions of alkynes (phenylacetylene, trimethylsilylacetylene 1-hexyne, 1,4-bis(trimethylsilylethynyl)benzene, and 1,4-bis(ethynyl)benzene) with hydrido nickel complexes (eq 1) bearing a [P, S]-ligand supported by trimethylphosphine were investigated (eq 2). Vinyl nickel complexes as the only products were obtained by the insertion reactions of alkynes into the Ni−H bonds.13b Recently, we have reported that vinyl nickel complexes or nickelacyclopropane complexes could be obtained by the insertion reaction of nickel hydride bearing a [P, Se]-ligand supported by trimethylphosphine with different alkynes (Scheme 1). [Ph2P(C 6H4)Se]NiH(PMe3)2 reacted with

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RESULTS AND DISCUSSION Synthesis of Hydrido Nickel(II) Complexes 1, 2, and 3. According to our early report for hydrido nickel complex 0,13b three novel hydrido nickel(II) complexes 1, 2, and 3 as S−H bond activation products containing the [P, S]-chelate ligands were obtained by the reaction of preligands L1, L2, and L3 with Ni(PMe3)4, respectively (eq 3). Complexes 1−3 were fully characterized by IR and NMR spectroscopy. In the IR spectra of complexes 1−3, the typical signals for the ν(Ni-H) vibration were found at 1897 (1), 1880 (2), and 1901 cm−1 (3), respectively. In comparison with that (ν(Ni-H) vibration, 1907 cm−1) of nickel(II) complex 0, the introduction of an electrondonating group (Me− (1), Me3Si− (2), and (3)) in the phenyl ring resulted in the bathochromic shift of the ν(Ni-H) vibration. In the 1H NMR spectra of complexes 1−3, the hydrido resonance appeared at −19.01 (1), −19.23 (2), and −19.14 ppm (3) as doublets with the JPH coupling constant of 27 (1), 39 (2), and 24 Hz (3), whereas the hydrido resonance in nickel complex 0 was recorded at −19.90 ppm. This small downfield shift was also caused by the introduction of the electron-donating group in the phenyl ring. In the 31P NMR spectra of complexes 1−3, there were two different phosphorus signals allocated to the diphenylphosphanyl group and trimethylphosphine ligands at 69.17, −8.47 ppm for 1, at 70.16, −8.48 ppm for 2, and at 70.17, −8.47 ppm for 3, respectively. All the spectroscopic information accords with a trigonal bipyramid coordination geometry. Single crystal X-ray diffraction confirmed the structures of complexes 1 (Figure 1) and 2 (Figure 2). In complex 1, the nickel atom is centered in a slightly distorted trigonal bipyramidal geometry with S1−Ni1−

Scheme 1. Reaction of Nickel Hydride Bearing a [P, Se]Ligand with Alkynes

phenylacetylene and 1-phenyl-1-propyne to give rise to the corresponding vinyl nickel complexes, [Ph2P(C6H4)Se]Ni(CPhCH2)(PMe3) and [Ph2P(C6H4)Se]Ni(CCH3CHPh)(PMe3)), under similar reaction conditions. Nevertheless, the insertion reactions of nickel hydride with diphenylacetylene, trimethylsilylacetylene, and 1-phenyl-2-(trimethylsilyl)acetylene afforded nickelacyclopropane complexes.14a In order to further understand the reaction rule and the related influence factor, in this work, three novel nickel(II) hydrides (1, 2, and 3) bearing [P, S]-chelate ligands were synthesized (eq 3). The reactions of nickel(II) hydrides (1, 2, and 3) with different alkynes were investigated. The experimental results show that the final products depend upon, on one hand, the substituents of the phenyl ring of the [P, S]-chelate ligand and, on the other hand, the substituents of the alkynes. It was concluded that the reactions of hydrido nickel complexes with alkynes could afford three different products: the known vinyl nickel complex, the known nickelacyclopropane complex, and the unexpected novel phenyl/vinyl exchange nickel complex. The third nickel compounds are new complexes that have never been reported before in the literature.

Figure 1. Molecular structure of complex 1. The thermal ellipsoids are displayed at 50% probability, and most hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ni1− H 1.39(3), Ni1−P1 2.1480(6), Ni1−P2 2.2032(7), Ni1−P3 2.1951(7), Ni1−S1 2.2447(7); S1−Ni1−H 170.8(12), P2−Ni1−P1 116.58(3), P3−Ni1−P1 126.96(3), P3−Ni1−P2 114.70(3). B


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Organometallics

Like hydrido nickel complex 0, complexes 1−3 in solution were also not stable at room temperature and they decomposed to bis-chelate nickel complexes within several minutes.13b Therefore, all of the reactions with complexes 1−3 were run at lower temperature without isolation of them. Reaction of Complex 1 with Phenylacetylene. Phenylacetylene was added to a mixture of L1 and Ni(PMe3)4 in THF at 0 °C. After workup, complex 4 was obtained as a yellow powder at −20 °C in 53% yield (eq 4). In the IR spectrum of 4, the v(CC) vibration signal was found at 1562 cm−1. In the 1 H NMR spectrum of 4, two vinyl protons were found at 4.73 and 5.78 ppm as singlets. In the 31P NMR spectrum of 4, there were two different phosphorus signals allocated to the diphenylphosphanyl group and trimethylphosphine ligand, which appeared at 50.89 and −13.20 ppm as doublets with the 2JPP coupling constant of 280 Hz. This big coupling constant indicates that the two P atoms are trans-positioned in solution. The spectroscopic data show that a Markovnikov addition took place. Complex 4 should have the similar structure to the vinyl nickel complexes obtained from the reactions of complex 0 with phenylacetylene, trimethylsilylacetylene, 1-hexyne, and 1,4-bis(trimethylsilylethynyl)benzene.13b The similar reactions of the corresponding selenium derivative compounds with phenylacetylene and 1-phenyl-1-propyne were also found.14a

Figure 2. Molecular structure of complex 2. The thermal ellipsoids are displayed at 50% probability, and most hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ni1− H 1.43(3), Ni1−P1 2.1385(4), Ni1−P2 2.1844(5), Ni1−P3 2.2324(6), Ni1−S1 2.2355(5); S1−Ni1−H 169.4(12), P2−Ni1−P1 134.34(2), P3−Ni1−P1 113.44(2), P3−Ni1−P2 110.57(2).

H (170.8(1)°) in the axial position. Three phosphorus atoms (P1, P2, and P3) are located in the equatorial plane with the total sum of coordination bond angles 358.24°, close to 360°. The Ni−H distance (1.39(3) Å) is within the range of known Ni−H bonds (1.37−1.50 Å).13a,15 Similarly, in the structure of complex 2, the axial angle of S1−Ni1−H was 169.4(1)°, deviating from 180°. The atoms of P1, P2, P3 were located in an equatorial plane with the total sum of the coordination bond angles 358.35°, close to 360°. The Ni−H distance (1.43(3) Å) was within the range of Ni−H bonds.13a,15 In both complexes 1 and 2, the chelate ring ([Ni1P1C2C1S1] (1) or

Reaction of Complex 2 or 3 with Phenylacetylene. If the trimethylsilyl group was introduced in the phenyl ring (L2 and L3), instead of hydrogen or methyl group (L0 and L1), two novel nickelacyclopropane complexes 5 and 6 were produced through the reactions of hydrides 2 and 3 with phenylacetylene under the similar reaction conditions (eq 5). In the 1H NMR spectra of 5 and 6, the CH2 protons were found

[Ni1P1C1C6S1] (2)) is perpendicular to the corresponding equatorial planes. The Ni−H distances in both complexes (1.39(3) Å (1) and 1.43(3) Å (2)) are shorter than that (1.50(3) Å) of complex 0.13b All of the three hydrido nickel complexes belong to trigonal bipyramidal geometry.

Scheme 2. Proposed Formation Mechanism of Complexes 5 and 6

C


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Organometallics

Reaction of Complex 1, 2, or 3 with Diphenylacetylene. Under the similar reaction conditions, the insertion of the Ni−H bond of complexes 1−3 with diphenylacetylene delivered nickelacyclopropane complexes 7, 8, and 9 as the only products (eq 6). In the 1H NMR spectra of complexes 7− 9, the NiCH proton was found at 3.02 ppm as a dd peak with the coupling constants of J = 24 and 6 Hz for 7, at 2.78 ppm as a dd peak with the coupling constants of J = 24 and 6 Hz for 8, and at 2.82 ppm as a dd peak with the coupling constants of J = 21 and 6 Hz for 9. In the 31P NMR spectra of complexes 7−9, there were two different phosphorus signals allocated to the diphenylphosphanyl group and trimethylphosphine ligand, which appeared at 64.39 and 20.62 ppm as doublets with the JPP coupling constant of 10.89 Hz for 7, at 63.22 and 20.71 ppm as doublets with the JPP coupling constant of 10.94 Hz for 8, and at 64.15 and 20.77 ppm as doublets with the JPP coupling constant of 10.94 Hz for 9. Single crystal X-ray diffraction verified that complexes 7 (Figure 3) and 9 (Figure 4) have a

at 1.83 ppm as a multiplet for 5 and at 2.35 ppm as a multiplet for 6. The chemical shifts of the methylene group imply that the carbon atom is in an sp3-hybridized state. In the 31P NMR spectra of 5 and 6, there were two different phosphorus signals allocated to the diphenylphosphanyl group and trimethylphosphine ligand, which appeared at 64.70 and 23.22 ppm as doublets with the JPP coupling constant of 8.5 Hz for 5 and at 70.93 and 23.29 ppm as doublets with the JPP coupling constants of 10.9 Hz for 6. In comparison with the related data of complex 4, these two JPP values are significantly smaller. This explains that the distances between the two phosphorus atoms are greater than two chemical bonds. On the basis of the NMR data and the literature reports,13,14a complexes 5 and 6 could be speculated as nickelacyclopropane complexes. The structures of complexes 5 and 6 are different from that of complex 4. This could be attributed to the introduction of the strong electrondonating group −SiMe3 at the phenyl ring.

In combination with the experimental results in this paper and the similar reports in the literature,9b,11,13,14a,16 we propose a reaction mechanism of formation of complexes 5 and 6 in Scheme 2. This process begins with the π-coordination of phenylacetylene after dissociation of one trimethylphosphine ligand to furnish the intermediate A5,6. The insertion of the πcoordinated CC bond into the Ni−H bond followed the Markovnikov rule to afford the vinyl nickel complex B5,6. The introduction of the strong electron-donating −SiMe3 group makes B5,6 unstable due to the increase in the density of the electron cloud on the nickel atom. Therefore, the reductive elimination between Ni−C and Ni−PMe3 bonds at the nickel center occurs to deliver intermediate C5,6 as a π-coordinated olefin complex with the formation of a quaternized phosphonium center. The nickelacyclopropane products 5 and 6 could be formed via oxidative addition of the π-bond of intermediate C5,6. Formally, C5,6 has a Ni(0) center, while complexes 5 and 6 are nickel(II) compounds. In this mechanism, the C−P reductive elimination was also referred to a 1,2-phosphine shift in the literature.9b,14a We think that it is better to call it reductive elimination, although this is not a general reductive elimination reaction because the two coordinated atoms (P and C) in the reductive elimination are neutral (P) and negatively charged (C). Generally, reductive elimination occurs between two anionic coordination atoms. The similar phenomenon was also found in the chemistry of the related selenium nickel complexes.14a In 1981, in the study of the mechanism of the insertion reaction of alkynes into the nickel−methyl bond, Bergman14b thought that phosphine could catalyze (cis/trans)-isomerization of the carbon−carbon double bond and the formation of phosphonium species might be related to this process, but he was not able to isolate them. Although we confirmed the formation of the phosphonium species in the study of insertion of alkyne into the Ni−H bond, we believe that our results support Bergman’s conclusions because the phenomenon and chemical principle are similar.

Figure 3. Molecular structure of complex 7. The thermal ellipsoids are displayed at 50% probability, and most hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ni1− S1 2.1812(1), Ni1−P1 2.1316(1), Ni1−C20 1.940(3), Ni1−C21 1.944(3), C20−C21 1.462(5), C20−P2 1.764(3); S1−Ni1−P1 92.48(4), C20−Ni1−S1 113.54(1), C21−Ni1−P1 109.57(1), C20− Ni1−C21 44.22(1), P2−C20−C21 116.4(2), P2−C20−C22 111.4(2), C21−C20−C22 123.4(3).

nickelacyclopropane structure. In complex 7, the ylidic bond distance C20−P2 is 1.764(3) Å, which is similar to our reported ylidic bond distance of Ph2P(C6H4)Se]Ni[Ph(PMe3)C−CHPh (1.770(3) Å).14a The C20−C21 bond (1.462(5) Å) is between C−C (1.53 Å) and CC (1.34 Å) and significantly longer than the typical distance (∼1.40 Å) in transition metal olefin complexes.9b The three bond angles ((P2−C20−C21 116.4(2)°), (P2−C20−C22 111.4(2)°), and (C21−C20−C22 123.4(3)°)) are closer to 120°, indicating that the C20 atom is inclined to be sp2-hybridized, although the four atoms [C21C20P2C22] are not in one plane. Therefore, it can be concluded that complex 7 is in a state between a nickelacyclopropane and a π-coordinated olefin nickel complex and more inclined to the former (Scheme 2). Complexes 9 and 7 have similar structural characteristics. D


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es,14a but created a new kind of phenyl nickel(II) complexes 13−15 (eq 8). In the 1H NMR spectra of complexes 13−15, the CH2 protons were found at 5.94 and 5.83 ppm for 13, at 5.98 and 5.87 ppm for 14, and at 5.94 and 5.60 ppm for 15. In the 31P NMR spectra of complexes 13−15, there were two different phosphorus signals allocated to the diphenylphosphanyl group and trimethylphosphine ligand, which appeared at 62.57 and −1.19 ppm as doublets with the JPP coupling constant of 287 Hz for 13, at 62.40 and −1.19 ppm as doublets with the JPP coupling constant of 288 Hz for 14, and at 60.13 and −1.16 ppm as doublets with the JPP coupling constant of 282 Hz for 15. Like complex 4, this big coupling constant implies that the distance between the two P atoms is two chemical bonds and the two P atoms are also trans-positioned in solution. Figure 4. Molecular structure of complex 9. The thermal ellipsoids are displayed at 50% probability, and most hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ni1− S1 2.1932(2), Ni1−P1 2.152(2), Ni1−C22 1.952(6), Ni1−C23 1.969(5), C22−C23 1.473(1), C22−P2 1.781(6); S1−Ni1−P1 91.25(7), C22−Ni1−S1 110.5(2), C23−Ni1−P1 114.2(2), C22− Ni1−C23 44.1(3), P2−C22−C23 114.9(4), P2−C22−C24 111.8(5), C23−C22−C24 124.5(5).

Single crystal X-ray diffraction confirmed the molecular structures of complexes 13 (Figure 5) and 14 (Figure 6). In

Reaction of Complex 1, 2, or 3 with 1-Phenyl-2trimethylsilylacetylene. As we expected, the insertion of 1phenyl-2-(trimethylsilyl)acetylene into the Ni−H bond of hydrido nickel complexes 1−3 delivered also nickelacyclopropane complexes 10, 11, and 12 (eq 7). In the 1H NMR spectra of complexes 10−12, the NiCH proton was found at 3.29 ppm for 10, at 3.57 ppm for 11, and at 3.41 ppm for 12. In the 31P NMR spectra of complexes 10−12, there were two different phosphorus signals allocated to the diphenylphosphanyl group and trimethylphosphine ligand, which appeared at 66.13 and 22.60 ppm as doublets with the JPP coupling constant of 10.89 Hz for 10, at 65.29 and 22.77 ppm as doublets with the JPP coupling constant of 10.94 Hz for 11, and at 64.63 and 24.66 ppm as doublets with the JPP coupling constant of 10.94 Hz for 12. It must be pointed out that the products of eq 7 have two possibilities. Based solely on the IR and NMR information, we cannot determine which one is the final product. For the similar selenium nickel complex, the spectroscopic data of two expected isomers as a 1:1 mixture were obtained.14a

Figure 5. Molecular structure of complex 13. The thermal ellipsoids are displayed at 50% probability, and most hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ni1− S1 2.1913(6), Ni1−P1 2.1629(5), Ni1−P2 2.1847(6), Ni1−C19 1.911(2), C1−C2 1.333(3); S1−Ni1−P1 90.04(2), P2−Ni1−S1 90.06(2), C19−Ni1−P1 90.51(6), C19−Ni1−P2 90.01(6).

complex 13, the nickel atom is centered in a square plane geometry with Ni1−S1 bond distance 2.1913(6) Å, Ni1−P1 bond distance 2.1629(5) Å, Ni1−P2 bond distance 2.1847(6) Å, and Ni1−C19 bond distance 1.911(2) Å. Two phosphorus atoms are situated in trans-positions. The bond distance of C1− C2 (1.333(3) Å) indicates that it is a double bond. The atoms of P1, P2, S1, C19, and Ni1 are located in one plane. The total sum of coordination bond angles is 360.62° close to 360°. The chelate ring [Ni1S1C6C7P1], phenyl ring [C6C7C8C9C11C12], and the square plane are in one plane. This plane is almost perpendicular to the phenyl plane [C19C20C21C22C23C24]. Both the sum of the bond angles (P1−C1−Si1 119.6(1)°, Si1−C1−C2 118.7(2)°, and C2−C1− P1 121.6(2)°) and the sum of the bond angles (H2A−C2−C1

Reaction of Complex 1, 2, or 3 with Trimethylsilylacetylene. To our surprise, the reactions between nickel hydrides 1−3 and trimethylsilylacetylene generated neither vinyl nickel complexes13b nor nickelacyclopropane complexE


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bond becomes possible. The similar methyl/phenyl exchange between a phosphine ligand and an alkyl ligand within one palladium complex was reported by Norton.17 However, this rearrangement does involve neither a phosphonium cation nor the requirement of phosphine dissociation. This point is different from the chemistry in this paper. Our experimental results indicate that the products of the reactions between the hydrido nickel complexes and alkynes depend upon the substituents both at the phenyl ring and of the alkynes. If the methyl group on the phenyl ring was replaced by the more electron-donating trimethylsilyl group, instead of the vinyl nickel complexes, the nickelacyclopropane complexes were formed; if phenylacetylene was replaced by diphenylacetylene or 1-phenyl-2-trimethylsilylacetylene, the nickelacyclopropane complexes were also delivered. With trimethylsilylacetylene, the phenyl/vinyl exchange nickel(II) complexes were obtained. In general, both the increase of the electron cloud density on the phenyl ring and the increase of the electron cloud density on the alkynes lead to the instability of the vinyl nickel complexes and promote the formation of nickelacyclopropane complexes or phenyl/vinyl exchange nickel complexes.

Figure 6. Molecular structure of complex 14. The thermal ellipsoids are displayed at 50% probability, and most hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ni1− S1 2.1886(4), Ni1−P1 2.1597(4), Ni1−P2 2.1833(4), Ni1−C24 1.9123(15), C10−C11 1.333(2); S1−Ni1−P1 88.495(16), P2−Ni1− S1 90.199(16), C24−Ni1−P1 92.25(4), C24−Ni1−P2 89.03(5).

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126(2)°, C1−C2−H2B 1234(2)°, and H2A−C2−H2B 111(3)°) are 359.9° and 360°, respectively. This shows that both C1 and C2 are in an sp2-hybridized state. Complex 14 as a derivative of 13 has the similar structural characteristics with 13. The mechanism of formation of complexes 13−15 is proposed in Scheme 3. As the formation of complexes 5 and 6, the first two steps are alkyne π-coordination and insertion of CC into the Ni−H bond to furnish intermediate B13−15. Unlike the mechanism in Scheme 2, the reductive elimination occurs between the Ni−Cvinyl and Ni−PPh2 bonds, not between Ni−Cvinyl and Ni−PMe3 bonds, to deliver intermediate C13−15 as a phosphonium salt. To our surprise, an oxidative addition of the P−Cphenyl bond at the nickel center(0) affords the final phenyl nickel(II) complexes 13−15 after the reductive elimination. The overall result is the exchange of phenyl and vinyl groups. This is because the strong electron-donating −SiMe3 group enhances the density of the electron cloud on the Ni atom. This results in the opening of the chelate ring via Cvinyl−PPh2 reductive elimination. Furthermore, the high electron cloud density at the nickel central atom increases its reducibility. Thus, the oxidative addition of the Cphenyl−PPh2

CONCLUSIONS Three new nickel(II) hydrides complexes (1, 2, and 3) were synthesized by the same method of the reactions of the derivatives of (2-diphenylphosphanyl)thiophenol with Ni(PMe3)4. The insertion reactions of alkynes into Ni−H bonds have been discussed. Normal vinyl nickel complex (4) was obtained by the reaction of phenylacetylene with 1. Eight nickelacyclopropane complexes (5−12) containing a ylidic ligand were isolated by the reactions of phenylacetylene, diphenylacetylene, and 1-phenyl-2-(trimethylsilyl)acetylene with 1, 2, and 3, respectively. Novel vinyl/phenyl exchange nickel complexes (13−15) were formed by insertion of trimethylsilylacetylene into the Ni−H bonds of 1, 2, and 3. To the best of our knowledge, complexes 13−15 were first obtained through the insertion of alkyne into Ni−H bonds. The results indicate that whether increasing the electronegativity on the benzene ring or on alkyne leads to the instability of the vinyl nickel complex, and is beneficial to the C−P reductive elimination to produce nickelacyclopropane complexes or phenyl nickel complexes via vinyl/phenyl exchange reaction in the case of the more electronegative nickel center. All of the complexes were fully detected by IR,

Scheme 3. Proposed Mechanism of Formation of Complexes 13−15

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Organometallics

132.9, 132.8, 132.4, 128.6, 25.9 (d, J = 14.3 Hz), 24.4 (d, J = 16.5 Hz), −1.06. Synthesis of Complex 4. A sample of Ni(PMe3)4 (0.58 g, 1.6 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(4-methyl)benzenethiol (0.49 g, 1.6 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, phenylacetylene (0.16 g, 1.6 mmol) was injected into the mixture. THF was removed under reduced pressure after the mixture was stirred for 3 days at 0 °C. The residue was extracted with pentane (30 mL) and diethyl ether (30 mL) to give a yellow solution. Complex 4 was obtained as a yellow powder at 20 °C. Yield: 0.46 g (0.85 mmol, 53%). Dec. > 124.5 °C. C30H32NiP2S (545.28 g/mol): calcd. C 66.08, H 5.91, S 5.88; found C 66.31, H 6.05, S 6.01. IR (Nujol mull, cm−1): 1586 v(CC), 1562 v(CC), 952 ρ(PMe3). 1H NMR (300 MHz, CDCl3, 298 K, ppm): 7.47−6.82 (m, 18H, Ar-H), 5.78 (s, 1H, C CH), 4.73 (s, 1H, CCH), 2.11 (s, 3H, Me), 1.28 (d, JPH = 9 Hz, 9H, PMe3). 31P NMR (121.5 MHz, CDCl3, 298 K, ppm): 50.99 (d, 2JPP = 280 Hz, 1P, PPh2), −13.19 (d, 2JPP = 280 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 146.3, 137.8, 136.6, 136.2, 133.3, 132.3, 132.2, 131.0, 130.7, 129.6, 129.4, 127.6, 127.3, 127.2, 126.0, 125.6, 118.3, 117.1, 29.9, 20.2, 15.4, 13.9. Synthesis of Complex 5. A sample of Ni(PMe3)4 (0.55 g, 1.5 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(6-trimethylsilanyl)benzenethiol (0.55 g, 1.5 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, phenylacetylene (0.15 g, 1.5 mmol) was injected into the mixture. THF was removed under reduced pressure after the mixture was stirred for 3 days at 0 °C. The residue was extracted with pentane (30 mL) and diethyl ether (30 mL) to give a yellow solution. Complex 5 was obtained as a yellow powder at 20 °C. Yield: 0.37 g (0.62 mmol, 41%). Dec. > 114.2 °C. C32H38NiP2SSi (603.44 g/mol): calcd. C 63.69, H 6.35, S 5.31; found C 63.91, H 6.49, S 5.49. IR (Nujol mull, cm−1): 1591 v(CC), 1553 v(CC), 974 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 7.47−6.71 (m, 18H, Ar-H), 1.83 (td, J = 6, 9 Hz, 2H, CH2), 0.69 (s, 9H, PMe3), 0.64 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 64.70 (d, 3JPP = 8.5 Hz, 1P, PPh2), 23.22 (d, 3JPP = 8.5 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 136.4, 134.9, 133.5, 133.3, 132.6, 132.4, 128.5, 127.6, 124.3, 122.0, 34.2, 22.4, 14.0, 0. 3. Synthesis of Complex 6. A sample of Ni(PMe3)4 (0.55 g, 1.5 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(4-trimethylsilanyl)benzenethiol (0.55 g, 1.5 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, phenylacetylene (0.15 g, 1.5 mmol) was injected into the mixture. THF was removed under reduced pressure after the mixture was stirred for 3 days at 0 °C. The residue was extracted with pentane (30 mL) and diethyl ether (30 mL) to give a yellow solution. Complex 6 was obtained as a yellow powder at 20 °C. Yield: 0.39 g (0.65 mmol, 43%). Dec. > 126.8 °C. C32H38NiP2SSi (603.44 g/mol): calcd. C 63.69, H 6.35, S 5.31; found C 63.42, H 6.55, S 5.59. IR (Nujol mull, cm−1): 1587 v(CC), 1561 v(CC), 953 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.44−7.02 (m, 18H, Ar-H), 2.39 (d, J = 6 Hz, 1H, CH), 2.30 (d, J = 6 Hz, 1H, CH), 0.91 (d, J = 12 Hz, 9H, PMe3), 0.25 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 70.93 (d, 3JPP = 10.9 Hz, 1P, PPh2), 23.29 (d, 3JPP = 10.9 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 137.4, 134.8, 134.0, 133.8, 133.6, 132.2, 132.0, 131.0, 129.9, 129.2, 128.5, 126.3, 125.7, 29.9, 11.1, 10.3, 1.0. Synthesis of Complex 7. Ni(PMe3)4 (0.73 g, 2.0 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(4-methyl)benzenethiol (0.62 g, 2.0 mmol) in 30 mL of THF at −78 °C. Diphenylacetylene (0.36 g, 2.0 mmol) in 10 mL of THF was added after the mixture was stirred for 1 h at 0 °C. The mixture was maintained at 0 °C for 2 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give an orange solution. Complex 7 was obtained as orange crystals at 20 °C. Yield: 0.94 g (1.52 mmol, 76%). Dec. > 107.3 °C. C36H36NiP2S (621.36 g/mol): calcd. C 69.57, H 5.84, S 5.16; found C 69.74, H 6.10, S 4.95. IR (Nujol mull, cm−1): 1588 v(CC), 946 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.34−6.87 (m, 23H, Ar-H), 3.02 (dd,

NMR. The molecular structures of complexes 1, 2, 7, 9, 13, and 14 were confirmed by single crystal X-ray diffraction.

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EXPERIMENTAL SECTION

General Procedures and Materials. All air-sensitive materials were prepared and manipulated under a nitrogen atmosphere by using a standard Schlenk technique. Diethyl ether, n-pentane, and THF were dried by distillation from Na-benzophenone under nitrogen before use. Phenylacetylene, (trimethylsilyl)acetylene, and dppp were purchased and used without further purification. Ni(PMe3)4,18 diphenylacetylene,19 and 1-phenyl-2-(trimethylsilyl)acetylene20 were prepared by the literature methods. Infrared spectra (4000−400 cm−1), as obtained from Nujol mulls between KBr disks, were recorded on a Bruker ALPHA FT-IR instrument. The 1H, 13C, and 31P NMR spectra (300, 75, 121 MHz, respectively) were recorded using Bruker Avance 300 MHz spectrometers with CDCl3 and C6D6 (without an internal reference) as the solvent at room temperature. 13 C and 31P NMR resonances were obtained with broadband proton decoupling. Elemental analyses were carried out on an Elementar Vario ELIII instrument. Melting points were measured with samples in capillaries sealed under nitrogen. Synthesis of Complex 1. A sample of Ni(PMe3)4 (1.095 g, 3.0 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(4-methyl)benzenethiol (0.83 g, 2.7 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, THF was removed under reduced pressure. The residue was extracted with pentane (50 mL) to give a red solution. Nickel hydride complex 1 was obtained as red crystals at −20 °C. Yield: 0.60 g (1.16 mmol, 43%). Dec. > 124.1 °C. C25H35NiP3S (519.21 g/mol): calcd. C 57.83, H 6.79, S 6.18; found C 58.10, H 6.90, S 6.08. IR (Nujol mull, cm−1): 1897 ν(Ni-H), 1587 v(CC), 939 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.00−6.76 (m, 13H, Ar-H), 1.89 (s, 3H, CH3), 1.26 (s, 18H, PMe3), −19.01 (d, JPH = 27 Hz, 1H, Ni-H). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 69.17 (s, 1P, PPh2), −8.47 (s, 2P, PMe3). 13 C NMR (75 MHz, C6D6, 298 K, ppm): 159.0, 143.5, 143.0, 142.3, 141.9, 141.9, 141.7, 141.5, 133.8, 133.7, 132.9, 132.8, 132.0, 131.4, 129.0, 25.9 (d, J = 14.3 Hz), 24.4 (d, J = 17.3 Hz), 20.50. Synthesis of Complex 2. A sample of Ni(PMe3)4 (1.059 g, 2.9 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(6-trimethylsilanyl)benzenethiol (0.965 g, 2.6 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, THF was removed under reduced pressure. The residue was extracted with pentane (50 mL) to give a red solution. Nickel hydride complex 2 was obtained as red crystals at −20 °C. Yield: 0.52 g (0.91 mmol, 35%). Dec. > 115.6 °C. C27H41NiP3SSi (577.37 g/mol): calcd. C 56.17, H 7.16, S 5.55; found C 56.02, H 6.99, S 5.68. IR (Nujol mull, cm−1): 1880 ν(Ni-H), 1551 v(CC), 942 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 7.75−6.93 (m, 13H, Ar-H), 1.12 (s, 18H, PMe3), 0.86 (s, 9H, SiMe3), −19.23 (d, JPH = 39 Hz, 1H, Ni-H). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 70.16 (s, 1P, PPh2), −8.48 (s, 2P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 168.0, 143.0, 142.8, 142.5, 142.3, 141.9, 141.5, 136.0, 134.3, 133.8, 133.4, 133.0, 132.9, 128.6, 120.0, 118.9, 25.8 (d, J = 13.5 Hz), 24.4 (d, J = 16.5 Hz), 0.00. Synthesis of Complex 3. A sample of Ni(PMe3)4 (1.095 g, 3.0 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(4-trimethylsilanyl)benzenethiol (0.998 g, 2.7 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, THF was removed under reduced pressure. The residue was extracted with pentane (50 mL) to give a red solution. Nickel hydride complex 3 was obtained as red crystals at −20 °C. Yield: 0.793 g (1.377 mmol, 51%). Dec. > 120.7 °C. C27H41NiP3SSi (577.37 g/mol): calcd. C 56.17, H 7.16, S 5.55; found C 56.40, H 7.29, S 5.80. IR (Nujol mull, cm−1): 1901 ν(Ni-H), 1564 v(CC), 937 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 7.87−6.93 (m, 13H, Ar-H), 1.13 (s, 18H, PMe3), 0.00 (s, 9H, SiMe3), −19.14 (d, JPH = 24 Hz, 1H, Ni-H). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 70.17 (s, 1P, PPh2), −8.47 (s, 2P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 164.0, 142.9, 142.6, 142.2, 142.0, 141.9, 141.7, 141.6, 136.8, 133.8, 133.7, 133.5, G


Article

Organometallics

ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.02−6.89 (m, 18H, Ar-H), 3.62 (s, 1H, NiCH), 0.89 (s, 9H, PMe3), 0.85 (s, 9H, SiMe3), 0.00 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 65.29 (d, 3JPP = 10.94 Hz, 1P, PPh2), 22.77 (d, 3JPP = 10.94 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 138.5, 137.4, 136.4, 136.1, 135.7, 134.9, 133.9, 132.9, 132.7, 132.7, 132.6, 127.8, 127.4, 127.2, 126.3, 120.0, 35.5, 30.0, 10.2 (d, J = 57 Hz), 1.6, 0.00. Synthesis of Complex 12. At −78 °C, (2-diphenylphosphanyl)(4-trimethylsilanyl)benzenethiol (0.73 g, 2.0 mmol) in 30 mL of THF was added to a solution of Ni(PMe3)4 (0.73 g, 2.0 mmol) in 50 mL of THF. 1-Phenyl-2-(trimethylsilyl)acetylene (0.35 g, 2.0 mmol) was added after the mixture was stirred for 1 h at 0 °C. The mixture was maintained at 0 °C for 2 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give an orange solution. Complex 12 was obtained as an orange powder at 20 °C. Yield: 0.81g (1.20 mmol, 60%). Dec. > 132.8 °C. C35H46NiP2SSi2 (675.55 g/mol): calcd. C 62.22, H 6.86, S 4.75; found C 62.45, H 6.66, S 4.49. IR (Nujol mull, cm−1): 1591 v(CC), 1561 v(CC), 948 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.12−6.86 (m, 18H, Ar-H), 3.41 (d, J = 3 Hz, 1H, NiCH), 0.78 (d, J = 15 Hz, 9H, PMe3), 0.15 (s, 9H, SiMe3), 0.00 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 64.63 (d, 3JPP = 10.94 Hz, 1P, PPh2), 24.66 (d, 3JPP = 10.94 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 165.1, 138.1, 134.8, 132.9, 132.8, 132.6, 132.5, 131.8, 131.8, 130.7, 130.6, 129.9, 129.9, 128.9, 128.3, 127.6, 127.2, 124.7, 54.3, 29.9, 14.5 (d, J = 2.25 Hz), 4.5, −1.1. Synthesis of Complex 13. To a solution of Ni(PMe3)4 (0.55 g, 1.5 mmol) in 50 mL of THF was added (2-diphenylphosphanyl)(4methyl)benzenethiol (0.46 g, 1.5 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, TMSA (0.15 g, 1.5 mmol) was injected into the mixture. The mixture was maintained at 0 °C for 3 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give a yellow solution. Complex 13 was obtained as yellow crystals at 20 °C. Yield: 0.52 g (0.96 mmol, 64%). Dec. > 97.3 °C. C27H36NiP2SSi (541.36 g/ mol): calcd. C 69.90, H 6.70, S 5.92; found C 70.21, H 6.59, S 6.17. IR (Nujol mull, cm−1): 1589 v(CC), 1548 v(CC), 952 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 7.75−6.66 (m, 13H, Ar-H), 5.94 (d, J = 24 Hz, 1H, CCH), 5.83 (d, J = 9 Hz, 1H, CCH), 1.88 (s, 3H, Me), 0.74 (d, J = 9 Hz, 9H, PMe3), 0.20 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 62.57 (d, 2JPP = 288 Hz, 1P, PPh2), −1.19 (d, 1P, 2JPP = 289 Hz, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 142.7, 138.2, 134.4, 133.9, 133.4, 133.0, 132.0, 130.6, 130.1, 129.8, 129.4, 129.2, 127.8, 121.4, 19.8, 16.4 (d, J = 35 Hz), 13.1 (d, J = 45 Hz), 2.0, 0.03. Synthesis of Complex 14. To a solution of Ni(PMe3)4 (0.62 g, 1.7 mmol) in 50 mL of THF was added (2-diphenylphosphanyl)(6trimethylsilanyl)benzenethiol (0.62 g, 1.7 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, TMSA (0.17 g, 1.7 mmol) was injected into the mixture. The mixture was maintained at 0 °C for 3 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give a yellow solution. Complex 14 was obtained as yellow crystals at 20 °C. Yield: 0.54 g (0.90 mmol, 53%). Dec. > 89.6 °C. C29H42NiP2SSi2 (599.52 g/mol): calcd. C 58.09, H 7.06, S 5.35; found C 58.33, H 6.88, S 5.34. IR (Nujol mull, cm−1): 1554 v(CC), 1505 v(CC), 926 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 7.45−6.77 (m, 13H, Ar-H), 5.98 (dd, J = 3, 9 Hz, 1H, CH), 5.87 (dd, J = 3, 9 Hz, 1H, CH), 0.77 (d, J = 9 Hz, 9H, PMe3), 0.64 (s, 9H, SiMe3), 0.20 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 62.40 (d, 3JPP = 288 Hz, 1P, PPh2), −1.19 (d, 2JPP = 288 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 166.1 (dd, J = 16.5, 36.8 Hz), 160.2, 143.4, 143.4, 138.7, 133.9, 129.6, 128.1, 128.0, 127.9, 122.0, 120.9, 16.7 (d, J = 35 Hz), 13.6 (d, J = 45 Hz), 2.0, 0.6, 0.00. Synthesis of Complex 15. To a solution of Ni(PMe3)4 (0.62 g, 1.7 mmol) in 50 mL of THF was added (2-diphenylphosphanyl)(4trimethylsilanyl)benzenethiol (0.62 g, 1.7 mmol) in 30 mL of THF at −78 °C. After the reaction mixture was stirred for 1 h at 0 °C, TMSA (0.17 g, 1.7 mmol) was injected into the mixture. The mixture was maintained at 0 °C for 3 days. After THF was removed, the solid was

JPH = 24, 6 Hz, 1H, NiCH), 2.05 (s, 3H, Me), 0.93 (d, JPH = 12 Hz, 9H, PMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 64.39 (d, 3JPP = 10.89 Hz, 1P, PPh2), 20.62 (d, 3JPP = 10.89 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 136.9, 135.5, 134.2, 133.6, 132.6, 132.0, 131.3, 131.1, 130.8, 127.6, 126.9, 123.4, 118.3, 29.9, 20.4, 10.5. Synthesis of Complex 8. Ni(PMe3)4 (0.55 g, 1.5 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(6trimethylsilanyl)benzenethiol (0.55 g, 1.5 mmol) in 30 mL of THF at −78 °C. Diphenylacetylene (0.27 g, 1.5 mmol) in 10 mL of THF was added after the mixture was stirred for 1 h at 0 °C. The mixture was maintained at 0 °C for 2 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give an orange solution. Complex 8 was obtained as orange crystals at 20 °C. Yield: 0.73 g (1.08 mmol, 72%). Dec. > 138.4 °C. C38H42NiP2SSi (679.47 g/mol): calcd. C 67.17, H 6.23, S 4.72; found C 66.83, H 6.09, S 4.50. IR (Nujol mull, cm−1): 1589 v(CC), 1553 v(CC), 950 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 7.43−6.61 (m, 23H, Ar-H), 2.78 (dd, J = 24, 6 Hz, 1H, NiCH), 0.74 (d, J = 6 Hz, 9H, PMe3), 0.69 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 63.22 (d, 3JPP = 10.94 Hz, 1P, PPh2), 20.71 (d, 3JPP = 10.94 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 146.5, 139.0, 138.9, 137.1, 136.2, 134.9, 134.1, 133.3, 133.1, 133.0, 131.8, 131.6, 130.0, 128.6, 127.1, 126.8, 125.8, 121.9, 119.9, 45.5, 10.5, 9.7, 0.00. Synthesis of Complex 9. Ni(PMe3)4 (0.55 g, 1.5 mmol) in 50 mL of THF was combined with (2-diphenylphosphanyl)(4trimethylsilanyl)benzenethiol (0.55 g, 1.5 mmol) in 30 mL of THF at −78 °C. Diphenylacetylene (0.27 g, 1.5 mmol) in 10 mL of THF was added after the mixture was stirred for 1 h at 0 °C. The mixture was maintained at 0 °C for 2 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give an orange solution. Complex 9 was obtained as orange crystals at 20 °C. Yield: 0.78 g (1.16 mmol, 77%). Dec. > 126.5 °C. C38H42NiP2SSi (679.47 g/mol): calcd. C 67.17, H 6.23, S 4.72; found C 66.96, H 5.97, S 4.88. IR (Nujol mull, cm−1): 1590 v(CC), 1563 v(CC), 949 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.22−6.66 (m, 23H, Ar-H), 2.82 (dd, JPH = 21, 6 Hz, 1H, NiCH), 0.71 (d, J = 12 Hz, 9H, PMe3), 0.00 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 64.15 (d, 3JPP = 10.94 Hz, 1P, PPh2), 20.77 (d, 3JPP = 10.94 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 165.4, 146.8, 137.7, 134.9, 133.5, 132.1, 130.9, 130.2, 126.2, 122.3, 46.0, 29.9, 10.5 (d, J = 57.75 Hz), −1.13. Synthesis of Complex 10. At −78 °C, (2-diphenylphosphanyl)(4-methyl)benzenethiol (0.49 g, 1.6 mmol) in 30 mL of THF was added to a solution of Ni(PMe3)4 (0.58 g, 1.6 mmol) in 50 mL of THF. 1-Phenyl-2-(trimethylsilyl)acetylene (0.28 g, 1.6 mmol) was added after the mixture was stirred for 1 h at 0 °C. The mixture was maintained at 0 °C for 2 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give an orange solution. Complex 10 was obtained as an orange powder at 20 °C. Yield: 0.70 g (1.14 mmol, 71%). Dec. > 119.7 °C. C33H40NiP2SSi (617.42 g/mol): calcd. C 64.19, H 6.53, S 5.19; found C 63.89, H 6.25, S 4.90. IR (Nujol mull, cm−1): 1590 v(CC), 945 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.23−6.92 (m, 18H, Ar-H), 3.29 (d, J = 6 Hz, 1H, NiCH), 1.97 (s, 3H, Me), 0.14 (s, 9H, PMe3), 0.00 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 66.13 (d, 3JPP = 10.89 Hz, 1P, PPh2), 22.60 (d, 3JPP = 10.89 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 144.6, 137.4, 134.0, 133.8, 133.6, 132.2, 132.0, 129.1, 128.5, 128.0, 127.6, 126.3, 119.0, 113.4, 29.9, 11.1 (d, J = 3 Hz), 10.3 (d, J = 3 Hz), −1.21 (d, J = 25.5 Hz). Synthesis of Complex 11. At −78 °C, (2-diphenylphosphanyl)(6-trimethylsilanyl)benzenethiol (0.73 g, 2.0 mmol) in 30 mL of THF was added to a solution of Ni(PMe3)4 (0.73 g, 2.0 mmol) in 50 mL of THF. 1-Phenyl-2-(trimethylsilyl)acetylene (0.35 g, 2.0 mmol) was added after the mixture was stirred for 1 h at 0 °C. The mixture was maintained at 0 °C for 2 days. After THF was removed, the solid was extracted with pentane (30 mL) and diethyl ether (30 mL) to give an orange solution. Complex 11 was obtained as an orange powder at 20 °C. Yield: 0.86 g (1.28 mmol, 64%). Dec. > 147.3 °C. C35H46NiP2SSi2 (675.55 g/mol): calcd. C 62.22, H 6.86, S 4.75; found C 62.36, H 6.75, S 4.56. IR (Nujol mull, cm−1): 1587 v(CC), 1552 v(CC), 947 H


Article

Organometallics

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extracted with pentane (30 mL) and diethyl ether (30 mL) to give a yellow solution. Complex 15 was obtained as yellow crystals at 20 °C. Yield: 0.57 g (0.95 mmol, 56%). Dec. > 101.3 °C. C29H42NiP2SSi2 (599.52 g/mol): calcd. C 58.09, H 7.06, S 5.35; found C 58.36, H 6.77, S 5.10. IR (Nujol mull, cm−1): 1559 v(CC), 956 ρ(PMe3). 1H NMR (300 MHz, C6D6, 298 K, ppm): 8.26−6.97 (m, 13H, Ar-H), 5.94 (s, 1H, CH), 5.60 (s, 1H, CH), 1.16 (d, J = 9 Hz, 9H, PMe3), 0.05 (s, 9H, SiMe3), 0.00 (s, 9H, SiMe3). 31P NMR (121.5 MHz, C6D6, 298 K, ppm): 60.13 (d, 2JPP = 282 Hz, 1P, PPh2), −1.16 (d, 2JPP = 282 Hz, 1P, PMe3). 13C NMR (75 MHz, C6D6, 298 K, ppm): 143.0, 142.9, 138.6, 138.6, 133.7, 133.6, 129.5, 127.9, 127.6, 127.5, 126.3, 121.8 (Ar-C), 22.0, 16.5 (d, J = 21.8 Hz), 13.5 (d, J = 23.3 Hz), 0.5, −1.2. X-ray Crystal Structure Determinations. Single crystal X-ray diffraction data of the complexes 1, 2, 7, 9, 13, and 14 were collected on a STOE STADIVARI Cu or Stoe IPDS2 diffractometer. Using Olex2,21 the structure was solved with the ShelXS22 structure solution program using Direct Methods and refined with the ShelXL23 refinement package using Least Squares minimization. .

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.7b00671. The table of selected crystallographic data and original IR, 1H NMR, 31P NMR, and 13C NMR spectra of the complexes (PDF) Accession Codes

CCDC 1490167, 1490169, and 1523252−1523255 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/ data_request/cif, or by emailing [email protected]. uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Xiaoyan Li: 0000-0003-0997-0380 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This paper is dedicated to Professor Dieter Fenske on the occasion of his 75th birthday. This work was supported by NSFC No. 21372143.

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REFERENCES

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