Reaction of Phenyl Iso(thio)cyanate with N-Heterocyclic Carbene

Article pubs.acs.org/Organometallics

Reaction of Phenyl Iso(thio)cyanate with N‑Heterocyclic CarbeneSupported Nickel Complexes: Formation of Nickelacycles Stefan Pelties and Robert Wolf* University of Regensburg, Institute of Inorganic Chemistry, D-93040 Regensburg, Germany S Supporting Information *

ABSTRACT: The nickel(I) complex [(η5-Cp)Ni(IPr)] (Cp = cyclopentadienyl, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin2-ylidene) reacts with phenyl isothiocyanate to afford the new heteronickelacycle [(IPr)NiSC(NPh)N(Ph)CS] (1), which contains the novel bidentate and dianionic ligand {SC(NPh)N(Ph)CS}2−. Complex 1 is also obtained from the nickel(0) compound [(IPr)Ni(styrene)2] with two equivalents of PhNCS. The γ-lactamnickelacycle [(IPr)NiN(Ph)C(O)CH2CH(Ph) (3) is formed from [(IPr)Ni(styrene)2] and one equivalent of phenyl isocyanate. Complex 3 is a rare example of a nickel(II) complex with a T-shaped structure. Compounds 1 and 3 were characterized by X-ray crystallography, 1H and 13C NMR spectroscopy, UV−vis spectroscopy, and elemental analysis.

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INTRODUCTION Mononuclear nickel(I) complexes, which display an open-shell electronic configuration, have been explored to a lesser extent compared to their di- and zerovalent analogues.1 Monovalent N-heterocyclic carbene (NHC) nickel complexes were first reported by Meyer and co-workers in 2004 and later by the group of Hillhouse in 2008.2,3 The chemistry of this class of complexes has attracted increasing interest recently.4 Hazari and co-workers prepared the first half-sandwich cyclopentadienyl and indenyl nickel(I) NHC complexes by chloride substitution of Sigman’s dimer [(NHC)Ni(μ-Cl)]2 with two equivalents of cyclopentadienyl sodium (Scheme 1a).5 Depending on the N-heterocyclic carbene and the type of cyclopentadienyl or indenyl ligand, mononuclear or metal−metal bonded dinuclear structures are formed. Some of these complexes are active catalysts of Suzuki− Miyaura cross-couplings. In an independent investigation, we found that the same type of [CpNi(NHC)] metalloradicals can be prepared by reducing [CpNiCl(NHC)] with KC8.6 [CpNi(IPr)] (A) reacts with P4, S8, Se∞, and Te∞, affording the nickel tetraphosphide [{CpNi(IPr)}2(μ-η1:η1-P4)], with a butterflyP42− ligand, and chalcogenides [{CpNi(IPr)}2(μ-E2)] (E = S, Se, Te) and [{CpNi(IPr)}2(μ-E3)] (E = S, Se) (Figure 1). Moreover, the square planar nickel(II) complex B with a side-on η2coordinated TEMPO ligand and a η1-coordinated Cp ligand was obtained in the reaction of complex A with the persistent radical TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidine 1-oxyl, Scheme 1a).6 In the course of these investigations, we became interested in examining the reactivity of [CpNi(IPr)] toward small unsaturated molecules. It is well known that in situ generated nickel(0) phosphane or NHC complexes mediate the cycloaddition of unsaturated organic compounds.7 This route represents a convenient © 2016 American Chemical Society

Scheme 1. (a) Synthesis and Reactivity of Cyclopentadienyl Nickel(I) Radicals;5,6 (b) Schematic of Nickel-Mediated Cycloaddition of Unsaturated Compounds

method for preparing (hetero)cyclic organic compounds and has attracted much attention.7 Metallacycles are presumed to be key Received: June 11, 2016 Published: August 8, 2016 2722

DOI: 10.1021/acs.organomet.6b00473 Organometallics 2016, 35, 2722−2727

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The molecular structure of 1 shows that two PhNCS molecules were coupled in the coordination sphere of nickel with the formation of a C−N single bond (C5−N3 1.442(3) Å), resulting in a dianionic {SC(NPh)N(Ph)CS}2− ligand, which coordinates to the [(IPr)Ni]2+ fragment (Figure 1). Numerous π- and σ-complexes of organyl isothiocyanates are known,10 and the insertion of organyl isothiocyanates into transition metal heteroatom bonds is also well documented.11 Nonetheless, a reductive dimerization of phenyl isothiocyanate in the coordination sphere of a transition metal has not been described previously to the best of our knowledge. The nickel atom is in a planar environment (sum of angles at Ni1 359.9°) formed by the carbene ligand, an η1-coordinated thiolate function [C5−S2 1.763(2) Å)], and a side-on η2-coordinated thiocarbonyl moiety [C4−S1 1.632(2) Å]. While the Ni1−S2 distance [Ni1−S2 2.1780(5) Å] is comparable to other square planar nickel(II) thiolates,12 the Ni1−S1 distance [Ni1−S1 2.3012(6) Å] is slightly longer, consistent with side-on coordination of the thiocarbonyl moiety. Furthermore, the N3−C4 bond distance [N3−C4 1.328(3) Å] is longer than the N4−C5 double bond [N4−C5 1.268(3) Å], presumably as a result of π-delocalization over S1, C4, and N3. A plausible reaction pathway for the formation of 1 from A and PhNCS is displayed in Scheme 3. Coordination of PhNCS

Figure 1. Solid-state molecular structure of [(IPr)Ni{SC(NPh)N(Ph)CS}] (1). The hydrogen atoms are omitted for clarity. Thermal ellipsoids are drawn at the 40% level. Selected bond lengths [Å] and angles [deg]: Ni1−S1 2.3012(6), Ni1−C4 1.763(2), Ni1−S2 2.1780(5), Ni1−C1 1.954(2), C4−S1 1.632(2), C5−S2 1.763(2), C5−N3 1.442(3), N3−C4 1.328(3), N4−C5 1.268(3), S1−Ni1−C4 44.97(6), C4−Ni1−S2 83.32(6), S2−Ni1−C1 113.69(6), C1−Ni1−S1 117.89(6), C4−N3− C6 124.06(17), C4−N3−C5 112.45(17), C5−N3−C6 122.96(16).

intermediates in these reactions.8 Ogoshi and co-workers isolated various nickelacycles by reacting in situ stoichiometric amounts of [Ni(1,5-cod)2] (1,5-cod = 1,5-cyclooctadiene), phosphanes, or NHCs with the unsaturated organic substrates (Scheme 1b).8 To the best of our knowledge the reactivity of well-defined nickel(I) NHC complexes toward heteroallenes has not been investigated. Here, we describe the reaction behavior of A with phenyl isocyanate and phenyl isothiocyanate. We report the synthesis and

Scheme 3. Proposed Mechanism of the Formation of 1

molecular structure of [(IPr)NiSC(NPh)N(Ph)CS] (1), formed by the reductive dimerization of two PhNCS molecules in the coordination sphere of nickel. In addition, we describe the

may induce a hapticity change for the Cp ligand from η5- to η1-coordination, forming intermediate D (Scheme 3, step (i)). A similar η1-Cp complex, [(η1-Cp)Ni(η2-TEMPO)(IPr)] (B, Scheme 1), was recently characterized.6 Subsequent Cp radical transfer from D to another molecule of A (Scheme 3, step (ii)) could yield complex 2 and a zerovalent nickel species that may react with PhNCS to give 1. The successful reaction of the nickel(0) complex [(IPr)Ni(styrene)2]13 (C) with two equivalents of PhNCS showed that a nickel(0) species could be involved. The reaction proceeds in a clean fashion according to 1H NMR, allowing complex 1 to be isolated in 47% yield as pure orange crystals (Scheme 2b). The compound is soluble in n-hexane, benzene, toluene, diethyl ether, and tetrahydrofuran. The 1H NMR spectrum of 1 (C6D6) corroborates the crystallographically determined structure. Two characteristic doublets at 1.07 and 1.52 ppm are assigned to the methyl groups of the 2,6-diisopropylphenyl (Dipp) substituents; the methine protons give rise to a septet at 2.83 ppm. A singlet at 6.53 ppm is detected for the protons of the imidazolin-2-ylidene backbone. The hydrogen atoms in meta- and para-position of the Dipp substituent and those of the phenyl groups are detected as five overlapping multiplets ranging from 6.75 to 7.37 ppm. The 13 C{1H} NMR spectrum features two signals for the C4 and C5 atoms (Figure 1) at 171.4 and 237.8 ppm. The carbene atom is detected at 189.9 ppm. The UV/vis spectrum of 1 in THF shows two intense absorptions at 284 and 325 nm, as well as two bands in the visible region at 413 and 519 nm. According to 1H NMR spectroscopy, a mixture of several unidentified diamagnetic species is formed in the reaction of A

preparation of [(IPr)NiN(Ph)C(O)CH2CH(Ph) (3), which was obtained by reacting PhNCO with [(IPr)Ni(styrene)2] (C). The synthesis of complex 3 demonstrates the reductive coupling of PhNCO with styrene in the coordination sphere of nickel.

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RESULTS AND DISCUSSION The reaction of A with one equivalent of phenyl isothiocyanate in THF (Scheme 2a) gave a mixture of 1 and the known bis(cyclopentadienyl) complex [(η5-Cp)(η1-Cp)Ni(IPr)] (2; see the SI for details).9 Attempts to separate compounds 1 and 2 by fractional crystallization remained unsuccessful. Scheme 2. Synthesis of Complex 1

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respectively, can be assigned to the diastereotopic methylene group in the γ-position of the metallacycle (Scheme 4b). It is noteworthy that the chemical shift of the high-field-shifted multiplet significantly changes with the solvent (δ(1H) = 0.30 ppm in C6D6 vs −0.46 ppm in THF-d8, Figure S2, SI). Methylene protons with a syn orientation with respect to vicinal organic substituents can show a significant high-field chemical shift compared to the anti-hydrogen atom.16 This probably explains the unusual high-field shift of one of the methylene signals. The magnetic anisotropy effect of the phenyl group attached to C6 might also contribute.17 On the basis of the high 1J(13C,1H) coupling constant (1J(13C,1H) = 130 Hz), which is in the typical range of sp3-CH2 groups, it seems unlikely that a C−H agostic interaction is the cause for the unusual high-field shift.18 1J(13C,1H) couplings in the range 75−100 Hz are expected for an agostic C−H bond. No hydrogen atom appears close enough to the vacant coordination site of the metal atom for an agostic interaction in the single-crystal X-ray structure, the closest contact being Ni1−H6 2.32(5) Å (Figure 2). A DFT optimization of the structure of 3 (BP86/def2-TZVP level, see the SI) is in good agreement with the crystallographically determined structure. The shortest Ni−H distance is Ni1−H6 2.47 Å. Closely related nickelacycles have been described by the groups of Yamamoto and Hoberg.19,20 Hoberg et al. synthesized a series of similar complexes by reacting Ni(cod)2, mono- and bidentate σ-donors, and organyl isocyanates with alkenes (Scheme 5), which were spectroscopically characterized.20 Some

Scheme 4. Synthesis of 3 from [(IPr)Ni(styrene)2]

toward PhNCO. Interestingly, the reaction of PhNCO with C (Scheme 4a) affords blue crystals of the nickel(II) complex 3 in 48% isolated yield. The molecular structure of 3 (Figure 2) features a γ-lactamnickelacycle derived from the coupling of one styrene and

Scheme 5. Heteronickelacycles Synthesized by Yamamoto and Hoberga19,20

Figure 2. Solid-state molecular structure of [(IPr)Ni{N(Ph)C(O)CH2CHPh}] (3). Only the S-enantiomer ((S)-3) is shown. The hydrogen atoms are omitted for clarity except for the hydrogen atoms attached to C5 and C6. Thermal ellipsoids are drawn at the 40% level. Selected bond length [Å] and angles [deg]; the analogous bond distances and angles of a second crystallographically independent molecule (R-isomer) in the asymmetric unit are given in brackets: Ni1−N1 1.876(4) [1.878(4)], Ni1−C6 1.945(5) [1.941(5)], Ni1−C1 1.879(4) [1.877(4)], Ni1−H6 2.32(5) [2.35(6)] N1−C4 1.356(6) [1.347(6)], C4−O1 1.227(6) [1.238(6)], C4−C5 1.518(6) [1.515(6)], C5−C6 1.521(7) [1.524(6)], N1−Ni1−C1 164.4(1) [164.6(1)], C1−Ni1−C6 104.0(2) [103.3(2)], N1−Ni1−C6 86.2(2) [86.5(2)].

a PhNCO molecule in the coordination sphere of nickel. The nickel atom features a distorted T-shaped environment [C1−Ni1−C6 104.0(2)°, N1−Ni1−C6 86.2(2)°, N1−Ni1−C1 164.4(2)°]. The nitrogen atom of the amide function is in a planar environment (∑angles = 358.8°). T-shaped d8 complexes, where the metal atom is purely surrounded by σ-donor ligands, are electronically favored over Y-shaped molecules,14 but wellcharacterized examples are rare. To our knowledge, only three, truely T-shaped three-coordinate nickel(II) species have been described, where there is no additional ligand or an agostic interaction at the fourth position of the square plane.3,4e,15 Crystalline 3 is only sparingly soluble in apolar solvents (n-hexane, benzene, and toluene), but it dissolves well in THF. The same compound can also be obtained in a lower yield (20%) by adding two equivalents of PhNCO to C in THF. According to 1H NMR spectroscopy, 3 slowly decomposes in THF-d8 over days at room temperature, forming the starting material, [(IPr)Ni(styrene)2] (C), and unidentified species. The 1H NMR spectrum of 3 (THF-d8, Figure S2, SI) displays one set of signals for the NHC ligand. A doublet at 2.82 ppm may be assigned to the C−H hydrogen atom adjacent to the nickel atom. Two doublets of doublets at 2.29 and −0.46 ppm,

a

dppe = 1,2-bis(diphenylphoshino)ethane, dcpe = 1,2-bis(dicyclohexylphosphino)ethane.

of these are intermediates in the nickel-catalyzed C−C coupling reactions of alkenes and isocyanates.20c,d Yamamoto et al. obtained very similar phosphane-stabilized nickel-containing amides by reacting Ni(cod)2 (cod = 1,5cyclooctadiene) with mono- and bidentate phosphanes and α,β-unsaturated amides (Scheme 5).19 Cryoscopic molecular weight determinations in benzene and a single-crystal X-ray structure analysis carried out for [(Et3P)Ni{N(H)C(O)CH(Me)CH2}], carrying a monodentate triethylphosphane ligand, revealed a tetrameric structure in the solid state and likely also in solution.19b The monomers are connected via the amide oxygen atom of a neighboring γ-lactam-nickelacycle. By contrast, the NHC complex 3 exists as a monomer due to the large steric demand of the diisopropylphenyl substituents on the NHC, which prevents further association. Complexes with bidentate phosphine ligands, e.g., 1,2-bis(diphenylphosphino)ethane (dppe), have tetracoordinate nickel centers and thus are monomers as well.19b,c 2724

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observed. After stirring the reaction mixture for 2 h at room temperature the solvent was removed and the residue was extracted with tetrahydrofuran (1 mL). Blue X-ray quality crystals formed by diffusion of n-hexane into the THF solution of 3. Yield: 93.3 mg (48%); mp > 170 °C (slow dec to a black solid). UV/vis (THF): λmax (nm, εmax / L·mol−1·cm−1) 296 (16 000), 354 (11 400), 699 (1100). Anal. Calcd for C42H49N3NiO (M = 670.57): C 75.23, H 7.37, N 6.27. Found: C 75.24, H 7.23, N 6.16. 1H NMR (THF-d8, 300 K, 400.13 MHz): δ (ppm) −0.46 (d, 3JHH = 16.8 Hz, 1H, PhCHCH2), 0.96 (d, 3JHH = 6.8 Hz, 6H, CH(CH3)2), 1.17 (d, 3JHH = 6.8 Hz, 6H, CH(CH3)2), 1.19 (d, 3JHH = 6.8 Hz, 6H, CH(CH3)2), 1.70 (d, 3JHH = 6.8 Hz, 6H, CH(CH3)2), 2.29 (dd, 3JHH = 7.7 Hz, 2JHH = 16.8 Hz, 1H, PhCHCH2), 2.49 (sept., 3JHH = 6.8 Hz, 2H, CH(CH3)2), 2.82 (d, 3JHH = 7.7 Hz, 1H, PhCHCH2), 3.85 (sept., 3JHH = 6.8 Hz, 2H, CH(CH3)2), 6.40 (d, JHH = 7.9 Hz, 2H, orthoCHNPh), 6.46 (t, JHH = 7.2 Hz, 1H, para-CHNPh), 6.57 (t, JHH = 7.6 Hz, 2H, meta-CHNPh), 6.90 (t, JHH = 7.6 Hz, 2H, meta-CHPhCH), 7.08 (d, JHH = 7.6 Hz, 2H, ortho-CHPhCH), 7.15 (t, JHH = 7.4 Hz, 1H, paraCHPhCH), 7.23 (d, JHH = 7.2 Hz, 2H, para-CHDipp), 7.44 (s, 2H, NCH of IPr), 7.52 (m, 2H, meta-CHDipp), 7.53 (m, 2H, meta-CHDipp). 13C{1H} NMR (THF-d8, 300 K, 100.61 MHz): δ (ppm) 14.5 (PhCHCH2), 23.6 (CH(CH3)2), 24.2 (CH(CH3)2), 25.4 (CH(CH3)2), 25.4 (CH(CH3)2), 29.3 (CH(CH3)), 30.2 (CH(CH3)), 46.6 (PhCHCH2), 120.0 (paraCHNPh), 120.5 (ortho-CHNPh), 123.4 (para-CHPhCH), 125.3 (para-CHDipp), 125.4 (meta-CHDipp), 126.2 (NCH of IPr), 127.1 (ortho-CHPhCH), 128.3 (meta-CHNPh), 130.3 (meta-CHPhCH), 131.1 (meta-ArDipp), 135.5 (Dipp), 146.5 (Dipp), 147.3 (Dipp), 149.1 (ipso-CNPh), 151.4 (ipso-CPhCH), 176.2 (CO), 178.9 (NCN of IPr). X-ray Crystallography. The single crystal X-ray diffraction data (Table S1) were recorded on an Agilent Technologies Gemini Ultra R diffractometer with microfocus Cu Kα radiation (λ = 1.541 84 Å). Empirical multiscan21 and analytical absorption corrections22 were applied to the data. Using Olex2,23 the structures were solved with SHELXT,24 and least-squares refinements on F2 were carried out with SHELXL.25 CCDC 1479160−1479162 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. DFT Calculations. The calculation on 3 was performed using the ORCA program package (version 3.0.2).26 The BP86 density functional and the Ahlrichs def2-TZVP basis set were employed for all atoms.27,28 The RI approximation was used.28,29 Ahlrichs Coulomb fitting basis for the TZVP basis for all atoms (TZV/J) and atom-pairwise dispersion correction to the DFT energy with Becke−Johnson damping (d3bj) were applied.30 The nature of the stationary point was verified by a numerical frequency analysis.

CONCLUSION In this paper, we have shown that the reaction of the nickel(I) radical [(η5-Cp)Ni(IPr)] (A) with one equivalent of PhNCS affords [(IPr)Ni{SC(NPh)N(Ph)CS}] (1), which features the new {SC(NPh)N(Ph)CS}2− dianion formed by dimerization of PhNCS in the coordination sphere of nickel. The reaction presumably involves the disproportionation of the nickel(I) species, which results in a reactive nickel(0) surrogate. Transfer of a Cp radical to a second equivalent of complex A affords the byproduct [(η5-Cp)(η1-Cp)Ni(IPr)] (2). Complex 1 can be cleanly accessed by reacting the nickel(0) compound [(IPr)Ni(styrene)2] (C) with two equivalents of PhNCS. The reaction of C with PhNCO afforded the new γ-lactamnickelacycle [(IPr)Ni{N(Ph)C(O)CH2CHPh}] (3) as a result of the reductive coupling of phenyl isocyanate and a styrene ligand. The solid-state molecular structure of monomeric 3 displays a rare T-shaped structure with a three-coordinate nickel atom. In future studies, it will be of interest to investigate whether similar reactions with other unsaturated substrates offer a general route toward NHC-stabilized heterometallacycles.

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EXPERIMENTAL SECTION

General Procedures and Starting Materials. All experiments were performed under an atmosphere of dry argon using standard Schlenk techniques or an MBraun UniLab glovebox. Solvents were dried and degassed with an MBraun SPS800 solvent purification system. Tetrahydrofuran and toluene were stored over molecular sieves (3 Å). Diethyl ether and n-hexane were stored over a potassium mirror. NMR spectra were recorded on Bruker Avance 300 and Avance 400 spectrometers at 300 K and internally referenced to residual solvent resonances. Melting points were measured on samples in sealed capillaries on a Stuart SMP10 melting point apparatus. UV/vis spectra were recorded on a Varian Cary 50 spectrophotometer. Elemental analyses were determined by the analytical department of Regensburg University. The starting materials [(C5H5)Ni(IPr)] and [(IPr)Ni(styrene)2] were prepared according to literature procedures.6,13 Phenyl isothiocyanate and phenyl isocyanate were purchased from commercial suppliers (PhNCS from ALFA Aesar and PhNCO from Sigma-Aldrich) and used as received. Synthesis of 1. A solution of phenyl isothiocyanate (58.8 mg, 0.435 mmol, 2.0 equiv) in toluene (∼2 mL) was added to a solution of [(IPr)Ni(styrene)2] (142.6 mg, 0.217 mmol, 1.0 equiv) in toluene (∼7 mL) at room temperature. An immediate color change from yellow to orange was observed. After stirring this solution for 2.5 h the solvent was removed in vacuo, and the residue was extracted with diethyl ether (5 mL). The filtrate was concentrated to 3 mL. Storage at room temperature for 18 h afforded orange X-ray quality crystals of 1 (58.9 mg). A second crop of crystalline 1 can be obtained after reducing the volume of the filtrate to 1 mL and storing the solution at −35 °C. Combined yield: 73.0 mg (47%); mp > 154 °C (dec to a black solid). UV/vis (THF): λmax (nm, εmax /L·mol−1·cm−1)) 284 (22 000), 325 (8700), 413 (4100), 519 (2200). Anal. Calcd for C42H46N4NiS2 (M = 717.66): C 69.14, H 6.35, N 7.68. Found: C 68.47, H 6.43, N 7.58. 1H NMR (C6D6, 300 K, 400.13 MHz): δ (ppm) 1.07 (d, 3JHH = 6.9 Hz, 12H, CH(CH3)2), 1.52 (d, 3JHH = 6.9 Hz, 12H, CH(CH3)2), 2.83 (sept., 3JHH = 6.9 Hz, 4H, CH(CH3)2), 6.53 (s, 2H, NC-H), 6.75−6.82 (m, 3H, CHPh), 6.99−7.04 (m, 3H, CHPh), 7.14 (m, 4H, meta-CHDipp), 7.23−7.30 (m, 4H, CHPh/para-CHDipp), 7.37 (m, 2H, CHPh). 13C{1H} NMR (C6D6, 300 K, 100.61 MHz): δ (ppm) 23.9 (CH(CH3)2), 25.1 (CH(CH3)2), 29.1 ((CHCH3)2), 122.9 (Ph), 123.2 (Ph), 123.8 (NCH), 124.3 (Dipp), 126.1 (Ph), 127.4 (Ph), 128.5 (Ph), 130.3 (Dipp), 136.7 (Dipp), 140.6 (Ph), 145.9 (Dipp), 149.7 (Dipp), 171.4 (NCS), 189.8 (NCN of IPr), 237.8 (NCS). Synthesis of 3. A solution of phenyl isocyanate (37.9 mg, 0.289 mmol, 1.1 equiv) in tetrahydrofuran (1 mL) was added to a solution of [(IPr)Ni(styrene)2] (189.6 mg, 0.318 mmol, 1.0 equiv) in tetrahydrofuran (3 mL) at room temperature. A color change from yellow to blue was

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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.6b00473.

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NMR spectra of 1 and 3 and details of the single-crystal X-ray structure analyses of 1−3 (PDF) Crystallographic data for 1−3 (CIF) (XYZ) (XYZ)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support by the Deutsche Forschungsgemeinschaft is gratefully acknowledged. 2725

DOI: 10.1021/acs.organomet.6b00473 Organometallics 2016, 35, 2722−2727

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DOI: 10.1021/acs.organomet.6b00473 Organometallics 2016, 35, 2722−2727

Article

Organometallics (29) (a) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098− 3100. (b) Perdew, J. P. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33, 8822−8824. (30) (a) Grimme, S.; Ehrlich, S.; Goerigk, L. J. Comput. Chem. 2011, 32, 1456−1465. (b) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104.

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DOI: 10.1021/acs.organomet.6b00473 Organometallics 2016, 35, 2722−2727