ARTICLE pubs.acs.org/Organometallics
Facile Synthesis of Organolanthanide Hydrides with Metallic Potassium: Crystal Structures and Reactivity Jie Zhang,* Weiyin Yi, Zhengxing Zhang, Zhenxia Chen, and Xigeng Zhou* Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China
bS Supporting Information ABSTRACT: A “new” strategy for the preparation of organolanthanide neutral hydrides by the reaction of organolanthanide chlorides with metallic potassium and their reactivity toward isocyanide has been studied. Treatment of [Me2Si(C5H4)2LnCl]2 with excess metallic potassium in THF results in a direct chlorine-abstracted reaction to yield the corresponding organolanthanide hydrides {μ-[η5-Me2Si(C5H4)2Ln]}2(μ-H)2 (Ln = Y (1), Er (2), Gd (3)) in moderate yields. Structural determination results indicated that complex 1 is a solvated neutral dimer with two bridging hydrogen atoms. Further investigations on their reactivity display that tert-butyl isocyanide (CNtBu) readily inserts into the Ln H bonds of 1 3 to form lanthanocene N-alkylformimidoyl complexes {μ-[η5-Me2Si(C5H4)2Ln]}2(μ,η2-HCdNCMe3)2 (Ln = Y (4), Er (5), Gd (6)). All compounds were characterized by elemental analysis and spectroscopic properties. The solid-state structures of complexes 1 and 4 6 were determined through X-ray single-crystal diffraction analysis.
’ INTRODUCTION Rare-earth metal hydrides continue to be a focus of much attention and have occupied a special place in organolanthanide chemistry because of their high activity and unique behavior in various catalytic processes.1 4 It has been confirmed that they are essential in catalysis and extensive applications in catalyzed hydrogenation or cyclization/silylation reactions of alkenes and alkynes.5 Recently, a few novel organolanthanide polyhydrido complexes and their intriguing reactivity have also been reported.6,7 However, most organolanthanide hydrides are synthesized through the hydrogenolysis or β-hydrogen elimination of their alkyl complexes.8 In view of this, we would like to develop some new synthetic routes to prepare organolanthanide neutral hydrides. Schumann et al. and Shen et al. previously reported that lanthanocene chlorides react with metallic sodium or lithium methylnaphthalene to yield lanthanocene hydride anionic “ate” complexes {Na(THF)6}{[(C5H5)2LuH]3H} and [Li(DME)3][(C5H5)3NdHNd(C5H5)3], respectively.9a,b Gambarotta et al. have also obtained a similar samarium hydride, {Na(THF)6}{([Ph2C(C4H3N)2]Sm)4(H)(THF)2}, by reaction of {[Ph2C(C4H3N)2]Sm}Cl with metallic sodium in THF.9c It is surprising that such an approach to produce lanthanide hydrides has not been further developed during the last twenty years. Noticeably, this route of preparing organolanthanide hydrides is more economical and simple than the hydrogenolysis or β-hydrogen elimination of organolanthanide alkyl complexes, if it can form alkali metal-free organolanthanide hydrides by the modulation of the appropriate reducing reagent and reaction conditions. In this contribution, we wish to report the synthesis of organolanthanide neutral hydrides through the reaction of organolanthanide chlorides with metallic potassium, which provides a simple and r 2011 American Chemical Society
feasible synthetic route to prepare alkali metal-free organolanthanide hydrides, and their reactivity toward tert-butyl isocyanide.
’ RESULTS AND DISCUSSION Synthesis and Reactivity of Organolanthanide Hydrides [Me2Si(C5H4)2LnH]2 (Ln = Y, Er, Gd). [Me2Si(C5H4)2LnCl]2
were allowed to react with excess metallic potassium in THF at room temperature, giving the lanthanide neutral hydrido complexes {μ2-[η5-Me2Si(C5H4)2Ln]}2(μ-H)2 (Ln = Y (1), Er (2), Gd (3)) in 40 50% isolated yields, as shown in Scheme 1. Structural determination results showed that 1 is a neutral centrosymmetric dimer, significantly different from that of [Na(THF)6][((C5H5)2LuH)3H], obtained by the reaction of [(C5H5)2LuCl]2 with metallic sodium or sodium amalgam in THF.9a The later was assumed to be an “ate” trinuclear complex, similar to that of [Li(THF)4][((C5H5)2YH)3H].10 It might be attributed to the following two factors: (i) the ionic radius of potassium ion K+ is larger than those of sodium ion Na+ and lithium ion Li+, so it is difficult for K+ to form ate-type complexes; (ii) the silyl-bridged cyclopentadienyl ligand is liable to coordinate with two lanthanide ions, forming binuclear complexes in the presence of small ligands such as H and Cl.11 Furthermore, in contrast to the reaction of (C5H5)2NdCl2Li(THF)2 with lithium methylnaphthalene to yield a ligand rearrangement product, [Li(DME)3][((C5H5)3NdHNd(C5H5)3],9b where these complexes were rearranged from a bis(cyclopentadienyl) moiety to a tris(cyclopentadienyl) moiety, the silyl-bridged cyclopentadienyl Received: May 10, 2011 Published: July 26, 2011 4320
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Scheme 1
ligands usually cannot undergo this rearrangement in many organometallic reactions.12 Noticeably, the formation of the alkali metal-free organolanthanide hydride complexes 1 3 is important, because only neutral metal hydrides are widely used for original reagents or catalysts.2 7 So this reaction can be adopted as a simple and feasible synthetic route to produce organolanthanide hydrides due to its easy handling and accessibility of starting materials. It should be noted that we choose the three rare-earth elements yttrium, erbium, and gadolinium based on the consideration of their strong Ln(III)/Ln(II) reduction potentials (g3.1 V vs NHE), which is higher than that of potassium (2.9 V vs NHE).13 Isocyanides are similar in their electronic structures to carbon monoxide, but have stronger σ-donor and weaker π-acceptor properties as an organic ligand. The reaction of organolanthanide hydrides with isocyanides can provide information on organolanthanide hydride reduction of carbon monoxide.14 With these organolanthanide hydrides 1 3 in hand, we next explored their reactivity toward isocyanide. 1 3 react with tert-butyl isocyanide in THF at ambient temperature to afford the expected products {μ2-[η5-Me2Si(C5H4)2Ln]}2(μ,η2-HCdNCMe3)2 (Ln = Y (4), Er (5), Gd (6)) in high yields, which are characterized as N-alkylformimidoyl complexes and similar to the reported compounds [(C5H5)2Ln(μ,η2-HCdNCMe3)]2 (Ln = Y, Er),15 indicating that tert-butyl isocyanide monoinserts readily into the Ln H bonds of 1 3. All of these compounds are air- and moisture-sensitive. They are readily dissolved in THF and toluene and slightly soluble in n-hexane. They were characterized by elemental analysis, IR, and/or 1H NMR spectra, which were in good agreement with the proposed structures. The 1H NMR spectrum of 1 contains resonances at δ 6.19, 6.07, 6.04, and 5.95 assignable to Me2Si(C5H4)2, at 0.30 assignable to Me2Si(C5H4)2, and at 3.54 and 1.47 assignable to the coordinated THF. The spectrum of 1 also exhibits a resonance at δ 1.70 as a triplet (JY H = 28 Hz) assignable to Y H Y due to coupling to two equivalent yttrium atoms.8c The IR spectraum of 1 displays a moderate absorption at 1340 cm 1 assignable to Y (μ-H) Y vibration.8c In the 1 H NMR spectrum of 4, a resonance at δ 9.34 is assigned to HCdNtBu,15 arising from hydrogen in the hydride starting
Figure 1. ORTEP diagram of {μ-[η5-Me2Si(C5H4)2Ln]}2(μ-H)2 (1) with probability ellipsoids drawn at the 30% level. Hydrogen atoms except the Y H bonds are omitted for clarity. Selected bond lengths (Å) and angles (deg):Y1 O1 2.389(10), Y1 Y1A 3.514(3) Y1 H1 2.04(7); C1 Si1 C8A 114.0(6). Symmetry transformations used to generate equivalent atoms: x+1, y+1, z.
Figure 2. ORTEP diagram of {μ-[η5-Me2Si(C5H4)2Ln]}2(μ,η2HCdNCMe3)2 (Ln = Y (4), Er (5), Gd (6)) with the probability ellipsoids drawn at the 30% level. For clarity, the silyl-bridged cyclopentadienyl and tert-butyl hydrogen atoms have been omitted.
material 1. Consistent with this observation, a characterized absorption at 1542 cm 1 in the IR spectrum of 4 is present, attributable to the CdN double bond stretching mode.16 The solid-state structures of complexes 1 and 4 6 were further confirmed by single-crystal X-ray diffraction analysis. Structural Description of Complexes 1 and 4 6. 1 crystallized from the solvent mixture of tetrahydrofuran and toluene at 20 °C in the monoclinic system, space group P21/c. The molecular structure and some important bond lengths and angles of 1 are shown in Figure 1. The X-ray structural analysis of 1 revealed the presence of a “flyover dimer”17 of composition 4321
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Table 1. Bond Lengths (Å) and Angles (deg) for 4 6a Ln = Y (4)
a
Ln = Er (5)
Ln = Gd (6)
Ln1 N1
2.285(6)
2.279(4)
2.288(6)
Ln1 C13
2.530(9)
2.521(5)
2.525(7)
Ln1 C13A
2.517(9)
2.518(5)
2.506(8)
N1 C13
1.296(9)
1.263(6)
1.285(9)
C13 H13
0.94(2)
0.939(19)
0.94(2)
N1 Ln1 C13A
122.7(2)
122.55(14)
122.7(2)
N1 Ln1 C13
30.7(2)
29.97(14)
30.5(2)
C13 Ln1 C13A N1 C13 Ln1A
92.0(3) 152.1(6)
92.59(14) 151.7(4)
92.3(2) 152.3(6)
N1 C13 Ln1
64.1(4)
64.4(3)
64.5(4)
Ln1 C13 Ln1A
88.0(3)
87.41(14)
87.7(2)
N1 C13 H13
120(5)
115(3)
115(5)
Ln1A C13 H13
87(4)
93(3)
93(5)
C4 Si1 C10A
117.2(4)
116.2(2)
116.6(3)
Symmetry transformations used to generate equivalent atoms: y, z+1.
x+1,
{μ2-[η5-Me2Si(C5H4)2Ln]}2(μ-H)2 as the predominant structural motif. It is known that single-atom-linked ansa-lanthanidocene complexes tend to abandon the chelating “wedge-type” binding mode in favor of this “spanning” coordination mode. Structurally characterized examples featuring this binding mode comprise [{Me2Si(C5H4)2Yb(μ-Cl)}2],18a [{Me2Si(C5H4)2Yb}2(μ-H)(μ-Cl)],12b [{Et2Si(C5H4)(3,4-Me2-C5H2)Lu(μ-H)}2],8a [{Et2Si(C5H4)(3,4-Me2-C5H2)Lu}2(μ-H)(μ-Et)],8a and [{Me2Si(3-Me3Si-C5H3)2Sm-(thf)(μ-H)}2].18b The spanning mode is particularly favored in the presence of small ligands such as H or Cl and sterically demanding linked cyclopentadienyl ligands. The bonding parameters of the [Y(μ-H)2Y] core respond extremely sensitively to repulsive metal 3 3 3 metal interactions; that is, they are sensitive to the metal size. The Y 3 3 3 Y distances and Y H bond lengths of 1 (3.514(3); 2.04(7) Å) are slightly shorter than those observed in other dimeric hydrido complexes such as [{(Me-C5H4)2Y(thf)(μ-H)}2] (3.66(1), 2.17(8), 2.19(8) Å)8c and [{(1,3-Me2-C5H3)2Y(thf)(μ-H)}2] (3.68(1), 2.03(7), 2.27(6) Å).18c The Y C(Cp ring) and Y O(THF) distances are in the normal range. X-ray determination indicates that complexes 4 6 are isostructural and are solvent-free dimeric structures, as shown in Figure 2. In each complex, the metal is surrounded by two cyclopentadienyl rings from two different silyl-bridged cyclopentadienyl units, a formimidoyl carbon nitrogen unit bonded edge-on, and a bridging carbon atom (C13) from the other formimidoyl ligand in the dimer. The six atoms Ln1, N1, C13, Ln1A, N1A, and C13A form an interlinked tricyclic structure via two bridged carbon atoms. Moreover, the six atoms plus C14 and C14A are planar within experimental error. The X-ray crystal data of complexes 4 6 were of sufficient quality to permit location of the unique hydrogen atoms H13 and H13A. The bond angles around C13 (sum = 360°) also indicate that the hydrogen position is roughly consistent with sp2 hybridization at the bridging carbon atom C13. In 5, the C13 N1 distance (1.263(6) Å) of the formimidoyl ligand is in the range of the value accepted for the N(sp2)d C(sp2) double bond (1.26 Å), indicating that the π-electrons of the CdN double bond in the present structure are localized. This distance is intermediate between the 1.24(1) Å length found in
the monometallic η1-complex Ru(η1-HCdNC6H4CH3)(CO)(PPh3)2(CH3CO2)19a and the 1.415(11) Å distances found in the trimetallic μ3,η2-complexes Os3(μ3,η2-HCdNPh)(CO)9H,19b in which the formimidoyl carbon and nitrogen atoms are bound to three different osmium atoms, and is comparable to the 1.262(8) and 1.288(7) Å lengths found in the bimetallic μ, η2-complex [(C5H5)2Er(μ,η2-HCdNtBu)]2.15 The Er1 C13 and Er1 C13A distances of 2.521(5) and 2.518(5) Å also are approximately equivalent to the corresponding values observed in [(C5H5)2Er(μ,η2-HCdNtBu)]2 (2.527(6), 2.532(6), 2.544(6), 2.490(6) Å) and compare well with the Ln C distances found in three-center, two-electron methyl-bridged organolanthanides. However, the Er1 N1 distance of 2.279(4) Å is intermediate between the values observed for a Er N single-bond distance and a Er N donor bond distance and is slightly shorter than those observed in [(C5H5)2Er(μ,η2-HCdNtBu)]2 (2.312(5) and 2.296(5) Å). These results indicate that the formimidoyl carbon still participates in a three-center, two-electron bridge, but it has more carbene than anionic character. The structural parameters of 4 and 6 (Table 1) are very similar to those for complex 5. The CdN distances of the formimidoyl ligand in 4 and 6 are 1.296(9) and 1.285(9) Å, respectively, and are slightly longer than those observed in 5. The Ln1 C13 and Ln1 N1 distances of 2.530(9) and 2.285(6) Å in 4 (Ln = Y) and 2.525(7) and 2.288(6) Å in 6 (Ln = Gd) are comparable to those observed in 5, when the differences in the metal ionic radii are considered.20
’ CONCLUSIONS We have demonstrated that rare-earth organometallic chlorides with the silyl-bridged bis-cyclopentadienyl ligand [Me2Si(C5H4)2] react with metallic potassium in THF to afford the corresponding neutral hydrides, providing a simple and useful method to synthesize alkali metal-free organolanthanide hydrides. Further investigations on their reactivity toward tert-butyl isocyanide suggest tBuNC inserts readily into the Ln H bond to construct a formimidoyl ligand (HCdNtBu), which binds with the lanthanide metals in a μ,η2-bonding mode. ’ EXPERIMENTAL SECTION General Procedures. All air- and moisture-sensitive manipulations were carried out using standard high-vacuum-line, Schlenk, or cannula techniques or in an MBraun inert atmosphere drybox containing an atmosphere of purified nitrogen. The solvents THF, toluene, and n-hexane were refluxed and distilled over sodium benzophenone ketyl under nitrogen immediately prior to use. [{Me2Si(C5H4)2Ln(μ-Cl)}2] (Ln = Y, Er, Gd) were prepared according to the procedures described in the literature.18a tert-Butyl isocyanide and metallic potassium were purchased from Aldrich and were used without purification. Elemental analyses for C, H, and N were carried out on a Rapid CHN-O analyzer. Infrared spectra were obtained on a Nicolet FT-IR 360 spectrometer with samples prepared as Nujol mulls. 1H NMR data were obtained on a Bruker DMX-400 NMR spectrometer and were referenced to residual aryl protons in C6H6 (δ 7.16). Synthesis of [Me2Si(C5H4)2YH(THF)]2 (1). Small potassium blocks (0.158 g, 4.00 mmol) were added to a 30 mL THF solution of [Me2Si(C5H4)2YCl]2 (1.03 g, 1.66 mmol) at room temperature. After stirring for 30 min, the clear, colorless solution slowly became turbid. After being stirred for 24 h at room temperature, the precipitates and residual metallic potassium were removed by the centrifugation. The solvent was removed under vacuum, and the solid residue was extracted with 30 mL of toluene. 4322
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Organometallics The yellow extract solution was concentrated and cooled at 20 °C to give a pale yellow powder. Recrystallization of the powder from the solvent mixture of THF and toluene gave 1 as colorless crystals. Yield: 0.484 g (42%). Anal. Calcd for C32H46O2Si2Y2: C, 55.17; H, 6.66. Found: C, 55.34; H, 6.76. IR (Nujol, cm 1): 3076(w), 1612(br), 1338(m), 1245(s), 1177(s), 1041(s), 945(m), 932(m), 768(s), 659(m). 1H NMR (C6H6): δ 6.19 (b, 4H, (C5H4)2Si(CH3)2), 6.07 (t, 4H, (C5H4)2Si(CH3)2), 6.04 (t, 4H, (C5H4)2Si(CH3)2), 5.95 (b, 4H, (C5H4)2Si(CH3)2), 3.54 (m, 8H, O(CH2CH2)2), 1.70 (t, 2H, Y H, JY H = 28), 1.47 (m, 8H, O(CH2CH2)2), 0.30 (s, 12H, (C5H4)2Si(CH3)2). Synthesis of [Me2Si(C5H4)2ErH(THF)]2 (2). Small potassium blocks (0.160 g, 4.00 mmol) were added to a solution of [Me2Si(C5H4)2ErCl]2 (1.43 g, 1.83 mmol) in 30 mL of THF at room temperature. The reaction mixture was subsequently worked up by the method described above. Pink crystals of 2 were obtained in 48% yield, 0.745 g. Anal. Calcd for C32H46O2Si2Er2: C, 45.04; H, 5.43. Found: C, 45.19; H, 5.51. IR (Nujol, cm 1): 3077(w), 1614(br), 1334(m), 1242(s), 1176(s), 1040(s), 944(m), 933(m), 770(s), 658(m). Synthesis of [Me2Si(C5H4)2GdH(THF)]2 (3). Following the procedure described for 1, reaction of [Me2Si(C5H4)2GdCl]2 (1.35 g, 1.78 mmol) with potassium blocks (0.158 g, 4.00 mmol) gave 6 as colorless crystals. Yield: 0.634 g (43%). Anal. Calcd for C32H46O2Si2Gd2: C, 46.12; H, 5.56. Found: C, 46.04; H, 5.46. IR (Nujol, cm 1): 3074(w), 1613(br), 1340(m), 1240(s), 1179(s), 1040(s), 943(m), 932(m), 770(s), 660(m). Synthesis of [Me2Si(C5H4)2Y(μ,η2-HCdNCMe3)]2 (4). tertButyl isocyanide (0.093 g, 1.12 mmol) was added dropwise to a 20 mL THF solution of 1 (0.390 g, 0.56 mmol) at room temperature. After stirring for 12 h, the solution was concentrated to about 5 mL and cooled at 20 °C to give colorless crystals of 4. Yield: 0.290 g (72%). Anal. Calcd for C34H48N2Si2Y2: C, 56.82; H, 6.73; N, 3.90. Found: C, 56.75; H, 6.60; N, 4.03. IR (Nujol, cm 1): 1610(br), 1542(m), 1365(s), 1307(w), 1285(m), 1243(s), 1170(s), 1035(s), 893(w), 847(m), 825(m), 807(m), 766(s), 667(m), 640(m). 1H NMR (C6H6): δ 9.34 (s, 2H, HCd NC(CH3)3), 6.35 (b, 4H, (C5H4)2Si(CH3)2), 6.15 (t, 8H, (C5H4)2Si(CH3)2), 5.75 (b, 4H, (C5H4)2Si(CH3)2), 1.12 (s, 9H, HCdNC(CH3)3), 0.30 (s, 12H, (C5H4)2Si(CH3)2). Synthesis of [Me2Si(C5H4)2Er(μ,η2-HCdNCMe3)]2 (5). tertButyl isocyanide (0.085 g, 1.26 mmol) was added to a solution of 2 (0.538 g, 0.63 mmol) in 30 mL of THF at room temperature. The reaction mixture was subsequently worked up by the method described above. Pink crystals of 5 were obtained in 83% yield, 0.458 g. Anal. Calcd for C34H48N2Si2Er2: C, 46.65; H, 5.53; N, 3.20. Found: C, 46.81; H, 5.58; N, 3.33. IR (Nujol, cm 1): 1611(br), 1541(m), 1367(s), 1304(w), 1286(m), 1242(s), 1168(s), 1034(s), 895(w), 848(m), 823(m), 808(m), 770(s), 668(m), 641(m). Synthesis of [Me2Si(C5H4)2Gd(μ,η2-HCdNCMe3)]2 (6). Following the procedure describled for 4, reaction of 3 (0.350 g, 0.42 mmol) with tert-butyl isocyanide (0.070 g, 0.84 mmol) gave 6 as colorless crystals. Yield: 0.275 g (77%). Anal. Calcd for C34H48N2Si2Gd2: C, 47.74; H, 5.56; N, 3.27. Found: C, 47.88; H, 5.64; N, 3.37. IR (Nujol, cm 1): 1613(br), 1542(m), 1363(s), 1305(w), 1288(m), 1241(s), 1170(s), 1037(s), 892(w), 847(m), 824(m), 810(m), 765(s), 663(m), 638(m).
X-ray Data Collection, Structure Determination, and Refinement. Suitable single crystals of complexes 1 and 4 6 were sealed under argon in Lindemann glass capillaries for X-ray structural analysis. Diffraction data were collected on a Bruker SMART Apex CCD diffractometer using graphite-monochromated Mo KR (λ = 0.71073 Å) radiation. During the intensity data collection, no significant decay was observed. The intensities were corrected for Lorentz polarization effects and empirical absorption with the SADABS program.21 The structures were solved by the direct method using the SHELXL-97 program.22 All non-hydrogen atoms were found from the difference Fourier syntheses.
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The H atoms were included in calculated positions with isotropic thermal parameters related to those of the supporting carbon atoms, but were not included in the refinement. All calculations were performed using the Bruker Smart program. Crystallographic data for 1: Mw = 696.69, monoclinic, space group P2(1)/c, a = 8.278(5) Å, b = 17.763(10) Å, c = 11.447(7) Å, β = 108.516(9)°, V = 1596.1(16) Å3, Z = 2, Dc = 1.450 g cm 3, μ(Mo KR) = 3.719 mm 1, F(000) = 720, 6510 reflections measured, 2806 unique (Rint = 0.2305), which was used in all calculations. Final R1 = 0.0968 and wR2 = 0.2084 (I > 2σ). For 4: Mw = 718.74, monoclinic, space group P2(1)/n, a = 11.188(10) Å, b = 15.142(13) Å, c = 11.414(10) Å, β = 116.736(12)°, V = 1727(3) Å3, Z = 2, Dc = 1.382 g cm 3, μ(Mo KR) = 3.438 mm 1, F(000) = 744, 7029 reflections measured, 3034 unique (Rint = 0.1549), which was used in all calculations. Final R1 = 0.0701 and wR2 = 0.1468 (I > 2σ). For 5: Mw = 875.44, monoclinic, space group P2(1)/n, a = 11.153(4) Å, b = 15.123(5) Å, c = 11.384(4) Å, β = 116.582(4)°, V = 1717.1(9) Å3, Z = 2, Dc = 1.693 g cm 3, μ(Mo KR) = 4.948 mm 1, F(000) = 860, 8226 reflections measured, 3747 unique (Rint = 0.0236), which was used in all calculations. Final R1 = 0.0320 and wR2 = 0.0656 (I > 2σ). For 6: Mw = 855.42, monoclinic, space group P2(1)/n, a = 11.161(4) Å, b = 15.137(5) Å, c = 11.403(4) Å, β = 116.640(5)°, V = 1880(2) Å3, Z = 2, Dc = 1.650 g cm 3, μ(Mo KR) = 3.912 mm 1, F(000) = 844, 7092 reflections measured, 3035 unique (Rint = 0.0505), which was used in all calculations. Final R1 = 0.0411 and wR2 = 0.0944 (I > 2σ).
’ ASSOCIATED CONTENT
bS
Supporting Information. Tables of atomic coordinates and thermal parameters, all bond distances and angles, and experimental data for all structurally characterized complexes. This material is available free of charge via the Internet at http:// pubs.acs.org.
’ AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected].
’ ACKNOWLEDGMENT We thank the National Natural Science Foundation of China, NSF of Shanghai (09ZR1403300), 973 Program (2009CB825300), and Shanghai Leading Academic Discipline Project (B108) for financial support. ’ REFERENCES (1) Reviews: (a) Ephritikhine, M. Chem. Rev. 1997, 97, 2193. (b) Schumann, H.; Meese-Marktscheffel, J. A.; Esser, L. Chem. Rev. 1995, 95, 865. (2) (a) Arndt, S.; Voth, P.; Spaniol, T. P.; Okuda, J. Organometallics 2000, 19, 4690. (b) Ringelberg, S. N.; Meetsma, A.; Troyanov, S. I.; Hessen, B.; Teuben, J. H. Organometallics 2002, 21, 1759. (c) Arndt, S.; Beckerle, K.; Hultzsch, K. C.; Sinnema, P.-J.; Voth, P.; Spaniol, T. P.; Okuda, J. J. Mol. Catal. A: Chem. 2002, 190, 215. (d) Kirillov, E.; Lehmann, C. W.; Razavi, A.; Carpentier., J.-F. Organometallics 2004, 23, 2768. (e) Trifonov, A. A.; Skvortsov, G. G.; Lyubov, D. M.; Skorodumova, N. A.; Fukin, G. K.; Baranov, E. V.; Glushakova, V. N. Chem.—Eur. J. 2006, 12, 5320. (f) Werkema, E. L.; Andersen, R. A.; Yahia, A.; Maron, L.; Eisenstein, O. Organometallics 2009, 28, 3173. (g) Takenaka, Y.; Hou, Z.-M. Organometallics 2009, 28, 5196. (h) Schupak, E. A.; Lyubov, D. M.; Baranov, E. V.; Fukin, G. K.; Suvorova, O. N.; Trifonov, A. A. Organometallics 2010, 29, 6141. (3) (a) Schmiege, B. M.; Ziller, J. W.; Evans, W. J. Inorg. Chem. 2010, 49, 10506. (b) Evans, W. J.; Schmiege, B. M.; Lorenz, S. E.; Miller, K. A.; 4323
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