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Synthesis, Structures, and Reactivity of Cyclometalated Complexes Formed by Insertion of Alkynes into M−C (M = Ir and Rh) Bonds Ruichen Sun, Shaowei Zhang, Xiaodan Chu, and Bolin Zhu* Tianjin Key Laboratory of Structure and Performance for Functional Molecules; Key Laboratory of Inorganic−Organic Hybrid Functional Material Chemistry, Ministry of Education; College of Chemistry, Tianjin Normal University, Tianjin 300387, PR China S Supporting Information *

ABSTRACT: Reactions of three aryl-substituted phosphines with [Cp*MCl2]2 (M = Ir and Rh) have been carried out in the presence of sodium acetate. Aryl-substituted phosphine is cyclometalated readily to give the corresponding five-membered metallacycle complex via an intramolecular activation of C(sp2)−H or C(sp3)−H bond. Competition reaction indicates that the aromatic C(sp2)−H bond is more likely to be activated than C(sp 3 )−H bond under the same conditions. As representatives of cyclometalated complexes containing an M− C(sp2) bond, cycloiridated complex 1 and cyclorhodated complex 3 reacted with DMAD to afford corresponding sevenmembered cyclometalated complexes 13 and 14 via 1,2-insertion of alkyne into M−C bond. However, the reaction of 1 with diphenylacetylene or phenylacetylene resulted in five-membered and six-membered doubly cycloiridated complexes 15 or 16, the formation of which presumably went through the vinylidene rearrangement of alkynes followed by 1,1-insertion; while the reaction of 3 with diphenylacetylene or phenylacetylene mainly gave normal seven-membered cyclorhodated complexes 17 or 18 by 1,2-insertion. For two representatives of cyclometalated complexes comprising an M−C(sp3) bond, cycloiridated complex 4 and cyclorhodated complex 6 reacted with DMAD to form corresponding seven-membered cyclometalated complexes 20 and 21 by 1,2-insertion. Interestingly, the reactions of 4 and 6 with phenylacetylene generated six-membered metallacycle complexes 22 and 23, and a plausible formation pathway is the similar 1,1-insertion of vinylidene ligand into the M−C bond followed by the isomerization of the C−C double bond. Molecular structures of five-membered cyclometalated complexes 4 and 5 and insertion products 13, 15−19, 21, and 22 were determined by X-ray diffraction.

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INTRODUCTION Cyclometalation using the transition metals iridium and rhodium is currently one of the most popular domain of cyclometalation, and a significant number of cyclometalated iridium and rhodium complexes have been prepared by heteroatom-assistant C−H bond activation.1,2 The reason that cycloiridation and cyclorhodation reactions have attracted such considerable attention is mainly due to the following facts: (i) Cyclometalated iridium complexes have important photophysical applications, i.e., as organic light-emitting devices (OLEDs)3 and photosensitizers.1d (ii) Cycloiridated complexes can be used as catalysts for a wide range of reactions, including water oxidation reaction,4 and alkane C−H oxidation.5 (iii) Cycloiridated and cyclorhodated complexes play an indispensable role in many catalytic cycles, especially rhodium-catalyzed reactions of 2-phenyl-substituted pyridines with different substrates, like alkenes,6 alkynes,7 or azides.8 (iv) The interesting and rich reactivities of the cycloiridated and cyclorhodated complexes, like insertion reactions of unsaturated molecules, i.e., alkyne, alkene, or carbon monoxide, into M−C bond,9 is usually an important step in the catalytic cycles mentioned above.7,10 We are particularly interested in the © XXXX American Chemical Society

insertion reactions of alkynes into M−C (M = Ir and Rh) bonds of cyclometalated complexes because they contribute to the understanding of catalytic mechanism of related reaction and the development of synthetic organic methods. To the best of our knowledge, the main types of insertion modes include 1,2-insertion, 1,1-insertion followed by vinylidene rearrangement, and sometimes a second insertion in either a 1,2- or a 1,1- pattern followed by a 1,2-insertion (Scheme 1). In this paper, we report synthesis and structures of a series of cyclometalated iridium and rhodium complexes starting from the precursor [Cp*MCl2]2 (M = Ir and Rh) and arylsubstituted phosphine or phosphinite ligands, as well as various insertion modes of alkynes into the M−C (M = Ir and Rh) bonds of five-membered cyclometalated complexes.

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RESULTS AND DISCUSSION Reactions of [Cp*MCl2]2 (M = Ir and Rh) with (1Naphthyl)diphenyl Phosphine. Reactions of [Cp*MCl2]2 (M = Ir and Rh) with (1-naphthyl)diphenyl phosphine in the Received: December 15, 2016

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DOI: 10.1021/acs.organomet.6b00933 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics Scheme 1. Survey of Insertion Reactions of Alkynes into M−Y Bond of Cyclometalated Complexes

presence of sodium acetate at room temperature result in corresponding five-membered cyclometalated complexes 1 (M = Ir) and 3 (M = Rh) in good yields (Scheme 2). Obviously,

Scheme 3. Reactions of [Cp*MCl2]2 (M = Ir and Rh) with Diisopropyl(o-methylphenyl) Phosphine

Scheme 2. Reactions of [Cp*MCl2]2 (M = Ir and Rh) with (1-Naphthyl)diphenyl phosphine

activation has been reported by Carmona group, and a typical reaction of [Cp*IrCl2]2 with phosphine PR(Xyl)2 was performed in the presence of 2,2,6,6-tetramethylpyperidine (TMPP).2l−p Complexes 4−6 were fully characterized by spectroscopic analysis, as well as crystallographic analysis for 4 and 5. The structure of 4 is shown in Figure 1, which reveals a classic three-legged piano stool geometry. The five-membered ring in the structure confirms the activation of a C(sp3)−H bond of a methyl group. Complex 5 exhibits a structure similar

the formation of complexes 1 and 3 goes through an intramolecular C(sp2)−H bond activation. In the case of [Cp*IrCl2]2, the reaction also affords small amount of complex 2, a normal phosphine-substituted iridium dichloride. Much longer time leads to the further conversion of 2 into 1, which indicates that the cyclometalation is a two-step process: First, the metal center is coordinated by the phosphine ligand; then, a geometrically accessible naphthyl C−H bond is activated by metal to form a metallacycle. The absence of a rhodium analogue of 2 shows that C−H bond activation by rhodium is much faster than that by iridium at the second step. An independent experiment, stirring a solution of 2 and sodium acetate in methanol at room temperature, further confirmed the conversion of 2 into 1. Complexes 1−3 were fully characterized by spectroscopic analysis. This type of heteroatom-assisted cyclometalation involving [Cp*MCl2]2 (M = Ir and Rh) has been widely reported recently, but in most cases, among all classic donors N is the major coordinating atom.9 Reactions of [Cp*MCl2]2 (M = Ir and Rh) with Diisopropyl(o-methylphenyl) Phosphine. Having demonstrated that phosphine ligand could act as a donor group for metalation of a naphthyl C(sp2)−H bond in complexes 1 and 3, we decided to test whether it could also promote activation of a C(sp3)−H bond. Reactions of [Cp*MCl2]2 (M = Ir and Rh) with diisopropyl(o-methylphenyl) phosphine in the presence of sodium acetate were carried out, which successfully afforded corresponding five-membered cyclometalated complexes 4 (M = Ir) and 6 (M = Rh) in good yields (Scheme 3). It is quite clear that the reactions realized the expected C(sp3)−H bond activation. Of particular note is that 4 is not quite air stable, which partially undergoes further oxidation to give complex 5 in the course of column chromatography purification. The type of cyclometalation reaction involving a C(sp3)−H bond

Figure 1. Thermal ellipsoid drawing of 4 showing the labeling scheme and 50% probability ellipsoids; hydrogens are omitted for clarity. Selected bond lengths [Å] and angles [°] are Ir(1)−P(1) 2.2651(11), Ir(1)−C(7) 2.119(5), P(1)−C(1) 1.803(5), C(1)−C(2) 1.394(7), C(2)−C(7) 1.511(7), Ir(1)−Cp(centroid) 1.860, ∠P(1)−Ir(1)−C(7) 81.66(13), ∠Ir(1)−P(1)−C(1) 105.25(16), ∠Ir(1)−C(7)−C(2) 116.6(3). B


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Organometallics

Reactions of [Cp*MCl2]2 (M = Ir and Rh) with (1Naphthyl)diisopropylphosphinite. In order to explore applicable scope of this type of cyclometalation, the ligand was extended to phosphinite. Therefore, reactions of [Cp*MCl 2 ] 2 (M = Ir and Rh) with (1-naphthyl)diisopropylphosphinite were examined, which produced corresponding five-membered cyclometalated complexes 9 and 11 (Scheme 5). Theoretically, another C(sp2)−H bond

to that of 4 in Figure 2, except that the methylene group was replaced by a carbonyl in the five-membered ring.

Scheme 5. Reactions of [Cp*MCl2]2 (M = Ir and Rh) with (1-Naphthyl)diisopropylphosphinite

at an adjacent α position of naphthyl ring could also be activated; however, no corresponding six-membered cyclometalated complex was detected. This regioselectivity of C−H bond activation should arise from the stability of fivemembered ring compounds as compared with six-membered ring compounds. It is interesting to note that the reactions also afforded methyl diisopropylphosphinite substituted iridium and rhodium dichloride 10 and 12. To track the source of methoxy in 10 and 12, the reactions mentioned above were performed in methanol-d4, which gave corresponding products 10-d3 and 12d3. This result indicated that methoxy group comes from the solvent methanol and that ligand-exchange between methoxy and 1-naphthoxy groups occurred in the reaction. Insertion of Alkynes into M−C(sp2) Bonds of Cyclometalated Complexes 1 and 3. Recently, insertion reactions of alkynes into transition metal−carbon bonds have attracted considerable attention in the field of organometallic chemistry, which is mainly due to the following factors: (i) The diversity of insertion mode of alkynes into M−C bond results in the various products with novel structures and interesting chemistry, including 1,2-insertion, 1,1-insertion, and double insertions (Scheme 1). (ii) In many alkyne-involved organic reactions catalyzed by transition metal complexes, the step that insertion of alkyne into M−C bond plays an integral part in the catalytic cycle; therefore, detailed study on the reactivity and regioselectivity of alkyne insertion would be very useful for understanding catalytic mechanism and designing new catalytic processes. With a series of cyclometalated complexes in hand, we first chose cycloiridated complex 1 and cyclorhodated complex 3 as representatives of containing M−C(sp2) bond, to study their reactivity of insertion of alkynes, so reactions of 1 and 3 with dimethyl acetylenedicarboxylate (DMAD) were tried, which underwent the normal 1,2-insertion and afforded corresponding seven-membered cyclometalated complexes 13 and 14 (Scheme 6). This result is consistent with most similar reactions of N-contained five-membered metallacycle with alkynes reported in literatures.9 13 and 14 were fully characterized by spectroscopic analysis, as well as crystallographic analysis for 13 (for the single crystal structure and crystallographic data of 13, see the Supporting Information). However, complexes 1 and 3 showed different reactivity and insertion modes when reacted with diphenylacetylene and phenylacetylene. Reactions of 1 with diphenylacetylene and

Figure 2. Thermal ellipsoid drawing of 5 showing the labeling scheme and 30% probability ellipsoids; hydrogens are omitted for clarity. Selected bond lengths [Å] and angles [°] are Ir(1)−P(1) 2.2683(12), Ir(1)−C(1) 2.031(5), P(1)−C(3) 1.815(5), C(2)−C(3) 1.382(8), C(1)−C(2) 1.515(7), C(1)−O(1) 1.231(6), Ir(1)−Cp(centroid) 1.889, ∠P(1)−Ir(1)−C(1) 80.48(15), ∠Ir(1)−P(1)−C(3) 102.27(18), ∠Ir(1)−C(1)−C(2) 117.7(4).

Reactions of [Cp*MCl2]2 (M = Ir and Rh) with Diisopropyl(2-methylnaphthyl) Phosphine. Since both C(sp2)−H and C(sp3)−H bonds could be activated in cyclometalation of [Cp*MCl2]2 with phosphines, we were curious about the relative activity between them. Therefore, diisopropyl(2-methylnaphthyl) phosphine was chosen as the ligand, which provides both C(sp2)−H and C(sp3)−H bonds at the appropriate positions, to test the competition reaction, and reactions of [Cp*MCl2]2 (M = Ir and Rh) with diisopropyl(2methylnaphthyl) phosphine under the above-mentioned conditions were performed, which selectively afforded corresponding five-membered cyclometalated complexes 7 and 8, the C(sp2)−H bond activated products (Scheme 4). This result indicated that aromatic C(sp2)−H bond activation is favored over C(sp3)−H bond activation, which is probably owing to the higher thermal stability of aryl hydrogen activated product when compared to alkyl hydrogen activated product. Complexes 7 and 8 were fully characterized by spectroscopic analysis. Scheme 4. Reactions of [Cp*MCl2]2 (M = Ir and Rh) with Diisopropyl(2-methylnaphthyl) Phosphine

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Organometallics Scheme 6. Insertion of DMAD into M−C(sp2) Bonds of 1 and 3

phenylacetylene in methanol at room temperature resulted in five- and six-membered doubly cyclometalated complexes 15 and 16 (Scheme 7), while reactions of 3 with diphenylacetylene and phenylacetylene in methanol produced corresponding seven-membered cyclometalated complexes 17 and 18 by means of normal 1,2-insertion mode. In the case of phenylacetylene, the reaction also afforded small amount of complex 19, the doubly six-membered cyclometalated complex. All five of products 15−19 were fully characterized by spectroscopic analysis as well as crystallographic analysis. The X-ray structures of 16 and 19 are depicted in Figures 3 and 4, and the crystal structures and crystallographic data for 15, 17, and 18 are provided in the Supporting Information. The structure of 16 shows that the iridium(III) center is coordinated by a η5 Cp*, one phosphorus atom P(1), and two metalated carbon atoms C(11) and C(18), which come from phenylacetylene. Two fused rings constitute the molecular framework: One is a five-membered ring, and the other is a sixmembered one. These share two adjacent atoms Ir(1) and C(18). For the five-membered ring, all five atoms in the ring are almost in the same plane. For the six-membered ring, the five nonmetal atoms are almost in one plane, while the metal atom Ir(1) is 1.514 Å away from the plane. By careful analysis of the crystal structures of 15 and 16, we found that one carbon atom is inserted into Ir−C(naphthyl) bond of 1, and the two phenyl groups in 15 are bound to the same carbon atom, which indicates that the migration of one phenyl group of diphenylacetylene occurs during the reaction. Besides, we also noticed that an ortho C−H bond of phenyl group from alkyne is activated by the iridium center. On the basis of the results described above, we proposed a plausible pathway for the formation of 15 or 16 in Scheme 8. First, the chloride of 1 dissociates to free up a coordinate space for aromatic alkyne and then generate a η2-alkyne complex A, which undergoes vinylidene rearrangement to give phenylvinylidene intermediate B. This is followed by 1,1-insertion of the vinylidene ligand into the Ir−C(naphthyl) bond to form C. In the last step, intramolecular activation of an ortho C−H bond of phenyl group occurs to build the second metallacycle, which comes with an elimination of HCl to afford the final

Figure 3. Thermal ellipsoid drawing of 16 showing the labeling scheme and 50% probability ellipsoids; hydrogens are omitted for clarity. Selected bond lengths [Å] and angles [°] are Ir(1)−P(1) 2.2329(8), Ir(1)−C(11) 2.045(3), Ir(1)−C(18) 2.058(3), C(11)− C(16) 1.417(4), C(16)−C(17) 1.450(5), C(17)−C(18) 1.353(4), C(18)−C(19) 1.472(4), C(19)−C(28) 1.439(5), C(27)−C(28) 1.443(5), P(1)−C(27) 1.826(3), Ir(1)−Cp(centroid) 1.909, ∠P(1)−Ir(1)−C(11) 92.89(9), ∠P(1)−Ir(1)−C(18) 75.30(9), ∠C(11)−Ir(1)−C(18) 78.42(13), ∠Ir(1)−P(1)−C(27) 103.34(11), ∠Ir(1)−C(18)−C(17) 116.2(2), ∠Ir(1)−C(18)−C(19) 119.1(2), ∠C(17)−C(18)−C(19) 124.6(3).

product 15 or 16. It is noteworthy that the similar complex of 15 or 16, in which N is the coordinating atom, has been reported by Ishii group; the synthetic procedure contains the reaction of five-membered cycloiridated complex with diphenylacetylene derivatives in the presence of NaBArF4, which affords a nine-membered iridacycle complex with a Ir(vinyl CH) agnostic interaction, followed by a further stirring in MeOH.9a However, in our case, NaBArF4 is not necessary for the initial dissociation of chloride. From the crystal structures of 17 and 18, we can tell that alkyne inserts into the Rh−C(naphthyl) bond in a 1,2- fashion. It is noteworthy that phenylacetylene undergoes the regioselective insertion to produce 18, which is mainly affected by the electronic factor. A similar situation has been discussed by Jones and co-workers in the reaction of N-contained cyclometalated iridium complex with phenylacetylene in MeOH.9d The structure of 19 shows that the rhodium(III) center is coordinated by a η5 Cp*, one phosphorus atom P(1), and two

Scheme 7. Insertion of Alkynes into M−C(sp2) Bonds of 1 and 3

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insertion of phenylacetylene into the M−C bond of Rh analogue of 16. However, we have never observed the formation of Rh analogue of 16 either by TLC monitoring of the reaction or by column chromatography, which may be attributed to the faster rate of the second 1,1-insertion as compared with the first one in the case of rhodium. With respect to the insertion of alkynes (including internal and terminal alkynes) into M−C bonds in the above system, there exists competition between 1,2-insertion and 1,1-insertion followed by vinylidene rearrangement. In the case of Ir−C(sp2) bond in 1, 1,1-insertion of alkynes followed by vinylidene rearrangement is more favored, while for Rh−C(sp2) bond in 3, 1,2-insertion pattern is a more preferred pathway for alkynes, although 1,1-insertion does occur when forming 19 but is not the major product. Insertion of Alkynes into M−C(sp3) Bonds of Cyclometalated Complexes 4 and 6. Cycloiridated complex 4 and cyclorhodated complex 6 were chosen as models containing M−C(sp3) bond to study the reactivity with alkynes. First, reactions of 4 and 6 with DMAD in methanol at room temperature were similarly carried out, which afforded corresponding seven-membered cyclometalated complexes 20 and 21 (Scheme 9). Comparing the reaction time and product

Figure 4. Thermal ellipsoid drawing of 19 showing the labeling scheme and 50% probability ellipsoids; hydrogens are omitted for clarity. Selected bond lengths [Å] and angles [°] are Rh(1)−P(1) 2.2361(15), Rh(1)−C(21) 2.046(6), Rh(1)−C(29) 2.046(6), P(1)− C(11) 1.827(6), C(11)−C(12) 1.420(10), C(12)−C(20) 1.441(8), C(20)−C(21) 1.490(8), C(21)−C(22) 1.357(9), C(22)−C(23) 1.458(8), C(23)−C(24) 1.395(10), C(24)−C(29) 1.490(9), C(29)−C(30) 1.360(10), Rh(1)−Cp(centroid) 1.924, ∠P(1)− Rh(1)−C(21) 77.64(17), ∠P(1)−Rh(1)−C(29) 91.65(17), ∠C(21)−Rh(1)−C(29) 89.6(2), ∠Rh(1)−P(1)−C(11) 103.8(2), ∠Rh(1)−C(21)−C(20) 118.5(4), ∠Rh(1)−C(21)−C(22) 124.0(4), ∠C(20)−C(21)−C(22) 117.4(5), ∠Rh(1)−C(29)−C(30) 120.8(5), ∠Rh(1)−C(29)−C(24) 117.4(4), ∠C(24)−C(29)−C(30) 121.5(5).

Scheme 9. Insertion of DMAD into M−C(sp3) Bonds of 4 and 6

Scheme 8. Plausible Pathway for Formation of 15 and 16

yield with the cases of 1 and 3, it is found that M−C(sp2) bonds show higher reactivity toward insertion of alkynes than M−C(sp3) bonds. The crystal structure of 21 is provided in the Supporting Information, which confirms the 1,2-insertion pattern of DMAD into Rh−C(sp3) bond of 6. Next, the reactions of 4 and 6 with phenylacetylene in methanol were conducted under the same conditions as with DMAD, and a similar 1,1-insertion or multiple-insertion pattern would be expected as in the cases of 1 and 3. Interestingly, the reactions did afford corresponding six-membered cyclometalated complexes 22 and 23 (Scheme 10), but not doubly cyclometalated complexes, like 15, 16, or 19. Through the spectroscopic and crystallographic analysis for 22 or 23, we observed that one carbon atom is inserted into Ir−C bond of 4, and the chloride is still bound to the transition metal atom. The most interesting feature of the crystal structure of 22 (Figure 5)

metalated carbon atoms C(21) and C(29). Two six-membered rings fused together sharing two adjacent atoms Rh(1) and C(21), which constitute the main molecular framework. For the six-membered ring (Rh(1)−P(1)−C(11)−C(12)−C(20)− C(21)), the five nonmetal atoms are almost in the same plane, while the metal atom Rh(1) is 1.456 Å away from the plane. For the other six-membered ring (Rh(1)−C(21)− C(22)−C(23)−C(24)−C(29)), the four carbon atoms C(22), C(23), C(24), and C(29) define a plane; the fifth carbon atom C(21) and metal atom Rh(1) are located on the same side of this plane. Of particular note in this context is the formation of 19, the doubly six-membered cyclometalated complex. On the basis of pathway we proposed for the formation of 15 and 16 in Scheme 8, we presume that 19 comes from the further 1,1-

Scheme 10. Insertion of Phenylacetylene into M−C(sp3) Bonds of 4 and 6

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in Scheme 10 also formed small quantities of unidentifiable byproducts. In addition, the reactions of 4 and 6 with diphenylacetylene were also carried out under the same conditions; unfortunately, the products are complicated mixtures. Attempts to isolate individual compounds by means of column chromatography were unsuccessful.

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CONCLUSIONS Cyclometalation reactions of a series of aryl-substituted phosphine or phosphinite with [Cp*MCl2]2 (M = Ir and Rh) were examined, and all of them generated stable five-membered cyclometalated iridium or rhodium complexes by P-assisted C− H bond activation. For two types of M−C bond in cyclometalated complexes: M−C(sp2) and M−C(sp3) bonds, aryl acetylenes exhibited different insertion modes. Even for the same type of M−C(sp2) bond, but with different metals, alkyne insertion modes are also different. In the case of the Ir−C(sp2) bond in 1, 1,1-insertion after the vinylidene rearrangement is more favored, while for the Rh−C(sp2) bond in 3, the 1,2insertion pattern is a more preferred pathway for alkynes. For M−C(sp3) bonds in cycloiridated complex 4 and cyclorhodated complex 6, phenylacetylene presented 1,1-insertion mode and then underwent a structural isomerization.

Figure 5. Thermal ellipsoid drawing of 22 showing the labeling scheme and 50% probability ellipsoids; hydrogens are omitted for clarity. Selected bond lengths [Å] and angles [°] are Ir(1)−P(1) 2.2666(10), Ir(1)−Cl(1) 2.4008(11), Ir(1)−C(24) 2.050(3), P(1)− C(17) 1.818(3), C(17)−C(22) 1.401(53), C(22)−C(23) 1.471(5), C(23)−C(24) 1.333(5), C(24)−C(25) 1.526(5), C(25)−C(26) 1.502(5), Ir(1)−Cp(centroid) 1.875, ∠P(1)−Ir(1)−C(24) 81.38(10), ∠P(1)−Ir(1)−Cl(1) 92.59(4), ∠C(24)−Ir(1)−Cl(1) 92.76(10), ∠Ir(1)−P(1)−C(17) 104.20(11), ∠Ir(1)−C(24)−C(23) 125.8(3), ∠Ir(1)−C(24)−C(25) 114.2(2), ∠C(23)−C(24)−C(25) 119.7(3), ∠C(22)−C(23)−C(24) 126.3(3).

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EXPERIMENTAL SECTION

General Considerations. All reactions were carried out under nitrogen using standard Schlenk and vacuum line techniques; however, the workup was carried out in air unless stated otherwise. All solvents were distilled from appropriate drying agents under nitrogen prior to use. 1H (400 MHz), 13C{1H} (100 MHz), and 31P{1H} (162 MHz) NMR spectra were recorded on a Bruker AV400 instrument at room temperature with CDCl3 as solvent. Chemical shifts were recorded in ppm, referenced to residual 1H and 13C signals of the nondeuterated CDCl3 (δ 7.26 and 77.16) as internal standards or to the 31P signal of PPh3 (δ −5.65) as an external standard. Elemental analyses were performed on a PerkinElmer 240C analyzer. IR spectra were recorded as KBr disks on a Nicolet 560 ESP FTIR spectrometer. The starting materials [Cp*MCl2]2 (M = Ir and Rh), DMAD, diphenylacetylene, and phenylacetylene were purchased from Strem without further purification; the ligands (1-naphthyl)diphenyl phosphine, 11 diisopropyl(o-methylphenyl) phosphine,12 diisopropyl(2-methylnaphthyl) phosphine,12 and (1-naphthyl)diisopropylphosphinite13 were prepared by literature methods. General Procedures for the Reactions of [Cp*MCl2]2 (M = Ir and Rh) with Phosphines or Phosphinite. A mixture of [Cp*MCl2]2 (M = Ir and Rh) (0.05 mmol), phosphine or phosphinite (2.0 equiv), and sodium acetate (4.0 equiv) in methanol (10 mL) was stirred for 1.5−4 h at room temperature. The solvent was then removed under vacuum, and the residue was chromatographed on a silica gel column with a mixture of petrol ether/diethyl ether as the eluent. The products were recrystallized from n-hexane/CH2Cl2 (1:1) at −10 °C to afford 1−12 as yellow, orange, or red crystals. 1. Reaction time 4 h, orange crystals (72% yield). 1H NMR: δ 8.04 (m, 2H), 7.82 (m, 1H), 7.71 (m, 1H), 7.67 (m, 1H), 7.46 (m, 5H), 7.35−7.22 (m, 4H), 6.97 (m, 2H), 1.57 (d, J = 2.0 Hz, 15H, Cp*). 13 C{1H} NMR: δ 151.2, 149.6, 139.2, 136.4, 135.9, 135.4, 133.3, 132.6, 132.3, 131.2, 130.8, 129.9, 129.8, 128.7, 128.6, 128.2, 128.0, 125.4, 94.6, 8.8. 31P{1H} NMR: δ 32.1. Anal. Calcd for C32H31ClIrP: C, 57.01; H, 4.63. Found: C, 57.22; H, 4.42. 2. Reaction time 4 h, red crystals (16% yield). 1H NMR: δ 8.58 (m, 1H), 7.97 (m, 1H), 7.89 (m, 1H), 7.82 (br, 2H), 7.49 (m, 1H), 7.38 (m, 2H), 7.29 (br, 8H), 7.16 (m, 1H), 1.16 (d, J = 2.0 Hz, 15H, Cp*). 13 C{1H} NMR: δ 135.2, 134.5, 134.2, 133.8, 132.3, 130.2, 130.1, 129.3, 128.8, 128.5, 128.0, 127.4, 126.7, 124.3, 92.8, 8.3. 31P{1H} NMR: δ 4.9. Anal. Calcd for C32H32Cl2IrP: C, 54.08; H, 4.54. Found: C, 54.25; H, 4.61.

is that a C(23)−C(24) double bond (1.333(5) Å) is formed when generating the six-membered metallacycle, while in the structures of 15 and 16 described above, a vinylidene carbon atom is inserted the Ir−C(naphthyl) bond when forming the six-membered ring. These results clearly demonstrate that the formation of 22 or 23 occurred through the similar 1,1insertion of vinylidene ligand into the M−C bond followed by the rearrangement of the CC double bond, and the plausible mechanistic pathway for the formation of 22 or 23 is proposed in Scheme 11. The first two steps are similar to the cases of 15 Scheme 11. Plausible Pathway for Formation of 22 and 23

and 16 in Scheme 8. The generated phenylvinylidene intermediate E undergoes 1,1-insertion of the vinylidene ligand and recoordination of chloride to form F, which isomerized to give final product 22 or 23 by 1,3-H shift. Interestingly, the further intramolecular activation of an ortho C−H bond of phenyl group to build the second metallacycle did not occur, even the independent reaction of 22 or 23 with base, like tBuOK, in methanol was performed. Besides, the reactions listed F


Article

Organometallics

δ 99.7, 53.6, 32.9, 18.6, 9.4. 31P{1H} NMR: δ 151.2. Anal. Calcd for C17H32Cl2OPRh: C, 44.66; H, 7.05. Found: C, 44.73; H, 7.14. General Procedures for the Insertion Reactions of Alkynes into M−C Bonds (M = Ir and Rh) of Cyclometalated Complexes 1, 3, 4, or 6. A mixture of cyclometalated complex (1, 3, 4, or 6) (0.02 mmol) and alkyne (4.0 equiv) in methanol (4 mL) was stirred for 0.5−24 h at room temperature. The solvent was then removed under vacuum ,and the residue was chromatographed on a silica gel column with a mixture of petrol ether/diethyl ether as the eluent. The products were recrystallized from n-hexane/CH2Cl2 or neat n-hexane at −10 °C to afford 13−23 as yellow, orange, or red crystals. 13. Reaction time 24 h, yellow crystals (73% yield). 1H NMR: δ 7.93 (m, 1H), 7.88 (m, 1H), 7.59−7.40 (m, 10H), 7.34 (m, 1H), 7.23 (m, 1H), 7.10 (m, 2H), 3.44 (s, 3H, CH3), 3.40 (s, 3H, CH3), 1.13 (d, J = 2.0 Hz, 15H, Cp*). 13C{1H} NMR: δ 179.2, 175.7, 142.8, 138.2, 133.2, 132.0, 131.5, 131.1, 129.9, 129.1, 128.3, 126.8, 126.7, 126.3, 125.6, 123.8, 123.7, 95.2, 53.6, 29.9, 8.1. 31P{1H} NMR: δ 5.2. Anal. Calcd for C38H37ClIrO4P: C, 55.91; H, 4.57. Found: C, 55.74; H, 4.45. 14. Reaction time 1.5 h, red crystals (86% yield). 1H NMR: δ 7.97 (m, 1H), 7.90 (m, 1H), 7.58−7.52 (m, 5H), 7.49−7.34 (m, 6H), 7.21 (m, 1H), 7.09 (m, 2H), 3.41 (s, 6H, CH3), 1.12 (d, J = 2.8 Hz, 15H, Cp*). 13C{1H} NMR: δ 173.6, 168.8, 138.1, 136.5, 134.4, 133.6, 133.3, 131.1, 130.6, 130.3, 129.2, 128.4, 128.2, 126.8, 126.3, 124.0, 101.5, 51.4, 29.9, 8.7. 31 P{ 1 H} NMR: δ 39.7. Anal. Calcd for C38H37ClO4PRh: C, 62.78; H, 5.13. Found: C, 62.55; H, 5.32. 15. Reaction time 24 h, yellow crystals (65% yield). 1H NMR: δ 7.90 (m, 1H), 7.78−7.40 (m, 3H), 7.59 (m, 1H), 7.58−7.26 (m, 9H), 7.09 (m, 1H), 7.03 (m, 1H), 6.88 (m, 2H), 6.72 (m, 2H), 6.66 (m, 2H), 6.37 (m, 1H), 6.17 (m, 2H), 1.30 (s, 15H, Cp*). 13C{1H} NMR: δ 173.4, 161.0, 157.0, 151.9, 151.3, 147.4, 143.8, 141.9, 137.0, 136.8, 135.6, 135.5, 133.7, 133.1, 131.9, 133.1, 131.9, 131.4, 131.0, 130.9, 130.5, 128.8, 128.4, 128.2, 127.9, 127.4, 126.8, 125.9, 125.0, 124.3, 124.0, 123.5, 120.8, 94.8, 8.6. 31P{1H} NMR: δ 12.6. Anal. Calcd for C46H40ClIrP: C, 64.89; H, 4.74. Found: C, 64.75; H, 4.62. 16. Reaction time 15 h, orange crystals (62% yield). 1H NMR: δ 7.93 (m, 1H), 7.77−7.66 (m, 4H), 7.49−7.43 (m, 6H), 7.37 (m, 1H), 6.85 (m, 1H), 6.71 (m, 3H), 6.63 (m, 1H), 6.53 (m, 2H), 6.06 (m, 2H), 1.33 (d, J = 1.6 Hz, 15H, Cp*). 13C{1H} NMR: δ 159.5, 157.6, 149.3, 146.2, 142.0, 137.2, 137.0, 136.7, 135.1, 134.3, 133.5, 132.8, 131.5, 130.9, 130.6, 128.1, 127.9, 127.6, 127.5, 126.9, 125.8, 125.1, 124.8, 124.4, 123.3, 122.7, 120.9, 119.9, 94.3, 8.8. 31P{1H} NMR: δ 14.4. Anal. Calcd for C40H36ClIrP: C, 61.96; H, 4.68. Found: C, 61.82; H, 4.73. 17. Reaction time 1 h, red crystals (69% yield). 1H NMR: δ 7.95 (m, 1H), 7.72 (m, 4H), 7.56−7.26 (m, 12H), 7.17 (m, 3H), 7.06 (m, 1H), 6.78 (m, 2H), 6.63 (m, 2H), 6.17 (m, 1H), 1.21 (d, J = 2.8 Hz, 15H, Cp*). 13C{1H} NMR: δ 151.6, 148.0, 143.6, 138.4, 137.4, 137.3, 136.4, 134.7, 133.6, 133.3, 132.2, 131.4, 131.3, 130.9, 130.6, 129.4, 128.9, 128.7, 127.9, 127.4, 126.6, 126.0, 125.1, 123.6, 101.2, 9.2. 31 1 P{ H} NMR: δ 44.0. Anal. Calcd for C46H41ClPRh: C, 72.40; H, 5.42. Found: C, 72.65; H, 5.33. 18. Reaction time 1 h, red crystals (55% yield). 1H NMR: δ 7.93 (m, 1H), 7.75 (m, 1H), 7.50 (m, 1H), 7.44 (m, 7H), 7.34−7.25 (m, 4H), 7.16 (m, 1H), 7.08 (m, 2H), 7.01 (m, 3H), 6.43 (m, 2H), 1.24 (d, J = 2.4 Hz, 15H, Cp*). 13C{1H} NMR: δ 152.1, 143.3, 138.4, 137.5, 136.2, 134.6, 133.1, 132.7, 131.6, 131.3, 131.2, 130.7, 130.3, 129.4, 129.0, 128.2, 128.0, 127.7, 126.6, 126.2, 125.2, 123.7, 101.0, 9.2. 31 1 P{ H} NMR: δ 42.7. Anal. Calcd for C40H37ClPRh: C, 69.93; H, 5.43. Found: C, 70.16; H, 5.25. 19. Reaction time 1 h, orange crystals (18% yield). 1H NMR: δ 7.90 (m, 1H), 7.77 (m, 1H), 7.66 (m, 3H), 7.52 (m, 4H), 7.31 (m, 1H), 7.13−7.05 (m, 4H), 7.01−6.79 (m, 12H), 6.61 (m, 1H), 1.15 (d, J = 2.4 Hz, 15H, Cp*). 13C{1H} NMR: δ 153.4, 148.5, 144.6, 137.0, 136.9, 134.7, 134.4, 131.4, 131.2, 129.6, 128.7, 128.5, 128.4, 128.3, 128.2, 127.7, 127.5, 126.9, 126.8, 126.6, 125.9, 125.5, 124.1, 123.9, 123.7, 122.7, 99.3, 8.8. 31P{1H} NMR: δ 42.9. Anal. Calcd for C48H42PRh: C, 76.59; H, 5.62. Found: C, 76.38; H, 5.57. 20. Reaction time 8 h, red crystals (56% yield). 1H NMR: δ 7.36− 7.29 (m, 4H, Ph), 3.86 (m, 2H, CH2), 3.71 (s, 3H, CH3), 3.62 (s, 3H, CH3), 3.59 (m, 1H, CH), 2.74 (m, 1H, CH), 1.61 (d, J = 2.0 Hz, 15H,

3. Reaction time 2 h, orange crystals (91% yield). 1H NMR: δ 8.12 (m, 2H), 7.85 (m, 1H), 7.72 (m, 2H), 7.49−7.36 (m, 6H), 7.32 (m, 1H), 7.25 (m, 2H), 6.98 (m, 2H), 1.53 (d, J = 2.8 Hz, 15H, Cp*). 13 C{1H} NMR: δ 149.5, 148.1, 138.9, 136.2, 135.7, 135.3, 132.8, 132.4, 132.2, 131.1, 130.5, 129.6, 129.5, 128.3, 128.2, 127.7, 127.5, 125.2, 100.7, 9.2. 31P{1H} NMR: δ 65.2. Anal. Calcd for C32H31ClPRh: C, 65.71; H, 5.34. Found: C, 65.46; H, 5.39. 4. Reaction time 2 h, orange crystals (54% yield). 1H NMR: δ 7.40 (m, 1H, Ph), 7.24 (m, 1H, Ph), 7.16 (m, 1H, Ph), 7.02 (m, 1H, Ph), 3.62 (d, J = 13.6 Hz, 1H, CH2), 3.08 (m, 1H, CH), 3.05 (d, J = 13.6 Hz, 1H, CH2), 2.01 (m, 1H, CH), 1.76 (d, J = 0.8 Hz, 15H, Cp*), 1.34−1.13 (m, 9H, CH3), 0.61 (dd, 3H, CH3). 13C{1H} NMR: δ 161.1, 134.5, 130.0, 129.9, 129.5, 124.1, 91.5, 27.5, 25.8, 20.1, 18.8, 18.2, 17.3, 17.1, 9.4. 31P{1H} NMR: δ 37.7. Anal. Calcd for C23H35ClIrP: C, 48.45; H, 6.19. Found: C, 48.64; H, 6.05. 5. Reaction time 2 h, pale yellow crystals (32% yield). 1H NMR: δ 7.77 (m, 1H, Ph), 7.60 (m, 1H, Ph), 7.42 (m, 2H, Ph), 3.32 (d, 1H, CH2), 2.22 (d, 1H, CH2), 1.79 (d, J = 1.6 Hz, 15H, Cp*), 1.39 (dd, 3H, CH3), 1.32 (dd, 3H, CH3), 1.20 (dd, 3H, CH3), 0.45 (dd, 3H, CH3). 13C{1H} NMR: δ 209.4, 168.5, 136.0, 133.9, 133.0, 131.9, 129.0, 97.2, 29.5, 25.3, 21.0, 20.0, 19.1, 17.6, 9.4. 31P{1H} NMR: δ 48.0. IR (νCO): 1620 (s) cm−1. Anal. Calcd for C23H33ClIrOP: C, 47.29; H, 5.69. Found: C, 47.35; H, 5.77. 6. Reaction time 1.5 h, orange crystals (83% yield). 1H NMR: δ 7.32 (m, 1H, Ph), 7.23 (m, 1H, Ph), 7.17 (m, 1H, Ph), 7.04 (m, 1H, Ph), 3.45 (m, 1H, CH2), 3.22 (m, 1H, CH2), 2.87 (m, 1H, CH), 2.21 (m, 1H, CH), 1.70 (d, J = 2.0 Hz, 15H, Cp*), 1.38 (dd, 3H, CH3), 1.24 (dd, 3H, CH3), 1.15 (dd, 3H, CH3), 0.74 (dd, 3H, CH3). 13 C{1H} NMR: δ 159.3, 132.9, 129.6, 129.5, 128.7, 124.2, 97.9, 30.6, 27.6, 26.3, 20.5, 19.0, 18.7, 17.6, 9.8. 31P{1H} NMR: δ 70.5. Anal. Calcd for C23H35ClPRh: C, 57.45; H, 7.34. Found: C, 57.63; H, 7.19. 7. Reaction time 4 h, yellow crystals (71% yield). 1H NMR: δ 7.63 (m, 1H), 7.50 (m, 1H), 7.27 (m, 1H), 7.17 (m, 2H), 3.40 (m, 1H, CH), 2.65 (s, 3H, CH3), 2.61 (m, 1H, CH), 1.75 (d, J = 1.6 Hz, 15H, Cp*), 1.50−1.40 (m, 6H, CH3), 1.20 (dd, 3H, CH3), 0.57 (dd, 3H, CH3). 13C{1H} NMR: δ 152.3, 148.4, 137.9, 136.7, 133.2, 131.9, 131.2, 128.6, 127.2, 121.3, 94.9, 29.9, 26.2, 23.3, 20.4, 19.9, 19.8, 19.4, 9.4. 31 1 P{ H} NMR: δ 51.9. Anal. Calcd for C27H37ClIrP: C, 52.29; H, 6.01. Found: C, 52.38; H, 6.24. 8. Reaction time 2 h, yellow crystals (87% yield). 1H NMR: δ 7.66 (m, 1H), 7.60 (m, 1H), 7.32 (m, 1H), 7.23 (m, 1H), 7.18 (m, 1H), 3.13 (m, 1H, CH), 2.64 (s, 3H, CH3), 2.62 (m, 1H, CH), 1.72 (d, J = 2.0 Hz, 15H, Cp*), 1.54−1.46 (m, 6H, CH3), 1.20 (dd, 3H, CH3), 0.62 (dd, 3H, CH3). 13C{1H} NMR: δ 164.7, 151.4, 138.1, 136.9, 132.0, 131.5, 131.1, 128.4, 126.7, 121.6, 100.9, 29.8, 28.9, 26.8, 23.2, 20.1, 19.8, 19.7, 9.9. 31P{1H} NMR: δ 90.7. Anal. Calcd for C27H37ClPRh: C, 61.08; H, 7.02. Found: C, 60.93; H, 7.15. 9. Reaction time 4 h, orange crystals (30% yield). 1H NMR: δ 7.99 (m, 1H), 7.71 (m, 1H), 7.42 (m, 1H), 7.35−7.21 (m, 3H), 3.33 (m, 1H, CH), 2.50 (m, 1H, CH), 1.83 (d, J = 1.6 Hz, 15H, Cp*), 1.46− 1.16 (m, 12H, CH3). 13C{1H} NMR: δ 158.5, 136.2, 132.4, 127.2, 124.6, 123.8, 123.3, 122.1, 121.5, 121.4, 95.1, 32.3, 30.6, 18.1, 17.6, 17.4, 17.2, 9.8. 31P{1H} NMR: δ 146.0. Anal. Calcd for C26H35ClIrOP: C, 50.19; H, 5.67. Found: C, 50.35; H, 5.48. 10. Reaction time 4 h, orange crystals (53% yield). 1H NMR: δ 3.58 (d, J = 10.4, 3H, CH3), 2.96 (m, 2H, CH), 1.63 (d, J = 2.0 Hz, 15H, Cp*), 1.39 (dd, 6H, CH3), 1.30 (dd, 6H, CH3). 13C{1H} NMR: δ 93.3, 54.4, 31.7, 18.3, 9.0. 31P{1H} NMR: δ 108.4. Anal. Calcd for C17H32Cl2IrOP: C, 37.36; H, 5.90. Found: C, 37.45; H, 6.03. 11. Reaction time 1.5 h, orange crystals (42% yield). 1H NMR: δ 7.93 (d, J = 8.4, 1H), 7.72 (d, J = 8.0, 1H), 7.48 (d, J = 8.4, 1H), 7.37 (d, J = 8.4, 1H), 7.35 (m, 1H), 7.27 (m, 1H), 3.08 (m, 1H, CH), 2.67 (m, 1H, CH), 1.75 (d, J = 2.8 Hz, 15H, Cp*), 1.46−1.35 (m, 9H, CH3), 1.27 (dd, 3 H, CH3). 13C{1H} NMR: δ 157.1, 139.5, 136.8, 132.6, 127.5, 124.8, 124.0, 121.9, 121.8, 121.5, 100.9, 32.1, 31.5, 18.2, 17.7, 17.4, 10.1. 31 P{ 1 H} NMR: δ 188.3. Anal. Calcd for C26H35ClOPRh: C, 58.60; H, 6.62. Found: C, 58.55; H, 6.79. 12. Reaction time 1.5 h, orange crystals (51% yield). 1H NMR: δ 3.66 (d, J = 10.4, 3H, CH3), 2.96 (m, 2H, CH), 1.63 (d, J = 3.2 Hz, 15H, Cp*), 1.41 (dd, 6H, CH3), 1.33 (dd, 6H, CH3). 13C{1H} NMR: G


Article

Organometallics Cp*), 1.17−1.11 (m, 6H, CH3), 1.00 (dd, 3H, CH3), 0.52 (dd, 3H, CH3). 13C{1H} NMR: δ 176.5, 165.5, 145.0, 136.2, 131.9, 131.7, 130.1, 126.3, 95.4, 51.6, 49.8, 41.9, 29.8, 25.4, 24.6, 22.6, 20.3, 20.2, 19.7, 10.0. 31P{1H} NMR: δ −2.5. Anal. Calcd for C29H41ClIrO4P: C, 48.90; H, 5.80. Found: C, 48.75; H, 5.72. 21. Reaction time 1 h, red crystals (63% yield). 1H NMR: δ 7.39− 7.29 (m, 4H, Ph), 3.79 (m, 2H, CH2), 3.69 (s, 3H, CH3), 3.63 (s, 3H, CH3), 3.41 (m, 1H, CH), 2.74 (m, 1H, CH), 1.62 (d, J = 2.8 Hz, 15H, Cp*), 1.25 (dd, 3H, CH3), 1.13 (dd, 3H, CH3), 1.05 (dd, 3H, CH3), 0.45 (dd, 3H, CH3). 13C{1H} NMR: δ 174.1, 163.8, 144.3, 134.9, 132.0, 131.4, 130.2, 126.6, 101.7, 51.7, 50.1, 41.8, 29.8, 25.6, 24.5, 22.4, 20.6, 20.1, 19.7, 10.6. 31P{1H} NMR: δ 33.5. Anal. Calcd for C29H41ClO4PRh: C, 55.91; H, 6.63. Found: C, 56.14; H, 6.57. 22. Reaction time 3 h, yellow crystals (37% yield). 1H NMR: δ 7.30 (m, 2H, Ph), 7.25−7.14 (m, 4H, Ph), 7.04 (m, 2H, Ph), 6.88 (m, 1H, Ph), 6.27 (m, 1H), 4.21 (m, 1H, CH2), 3.45 (m, 1H, CH2), 3.00 (m, 1H, CH), 2.71 (m, 1H, CH), 1.72−1.60(m, 6H, CH3), 1.53 (dd, 3H, CH3), 1.39 (d, J = 1.6 Hz, 15H, Cp*), 0.80 (dd, 3H, CH3). 13C{1H} NMR: δ 148.9, 148.3, 143.4, 130.1, 129.4, 129.0, 128.1, 127.0, 126.4, 126.0, 125.3, 123.4, 93.3, 52.4, 32.1, 29.5, 27.9, 23.7, 22.9, 21.8, 21.4, 19.4, 8.2. 31P{1H} NMR: δ 12.6. Anal. Calcd for C31H41ClIrP: C, 55.38; H, 6.15. Found: C, 55.26; H, 6.23. 23. Reaction time 0.5 h, red crystals (55% yield). 1H NMR: δ 7.33− 7.28 (m, 3H), 7.21−7.05 (m, 5H, Ph), 6.90 (m, 1H, Ph), 6.26 (m, 1H), 4.27 (m, 1H, CH2), 3.72 (m, 1H, CH2), 2.82 (m, 2H, CH), 1.73−1.66 (m, 6H, CH3), 1.51 (dd, 3H, CH3), 1.36 (d, J = 2.4 Hz, 15H, Cp*), 0.85 (dd, 3H, CH3). 13C{1H} NMR: δ 147.3, 147.2, 142.6, 129.9, 129.5, 129.4, 128.5, 128.2, 126.5, 125.4, 125.0, 124.4, 99.8, 52.4, 32.1, 29.5, 28.1, 24.4, 22.8, 22.3, 21.9, 21.0, 19.9, 8.7. 31P{1H} NMR: δ 53.6. Anal. Calcd for C31H41ClPRh: C, 63.87; H, 7.09. Found: C, 63.76; H, 6.92. Crystallographic Studies. Single crystals of complexes 4, 5, 13, 17, 18, 21, and 22 suitable for X-ray diffraction were obtained by crystallization from n-hexane/CH2Cl2 (1:1), and single crystals of complexes 15, 16, and 19 were obtained by crystallization from pure nhexane. Data collection was performed on a Bruker SMART 1000, using graphite-monochromated Mo Kα radiation (ω−2θ scans, λ = 0.71073 Å). Semiempirical absorption corrections were applied for all complexes. The structures were solved by direct methods and refined by full-matrix least-squares. All calculations were using the SHELXTL97 program system. The crystal data and summary of X-ray data collection are presented in Tables S1−S3.

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21572160), the Natural Science Foundation of Tianjin (14JCYBJC20300), and the Program for Innovative Research Team in University of Tianjin (TD12-5038).

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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.6b00933. Crystallographic details for complexes 4, 5, 13, 15−19, 21, and 22 (CIF) 1 H NMR and 31P NMR spectra of complexes 1−23, single crystal structures of 13, 15, 17, 18, and 21 (including selected bond lengths and angles), crystallographic data tables (PDF)

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REFERENCES

AUTHOR INFORMATION

Corresponding Author

*Fax: 86-22-23766532. E-mail: [email protected]. ORCID

Bolin Zhu: 0000-0002-6846-566X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge financial support from the National Natural Science Foundation of China (21002069 and H


Article

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