Nickel(I) monomers and dimers with cyclopentadienyl and indenyl ligands

Jianguo Wu, Ainara Nova, David Balcells, Gary W Brudvig, Wei Dai, Louise M. Guard, Nilay Hazari, Po Heng Lin, Ravi Pokhrel, Michael K. Takase

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Abstract

The reaction of (μ-Cl)2Ni2(NHC)2 (NHC=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IPr) or 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr)) with either one equivalent of sodium cyclopentadienyl (NaCp) or lithium indenyl (LiInd) results in the formation of diamagnetic NHC supported NiI dimers of the form (μ-Cp)(μ-Cl)Ni2(NHC)2 (NHC=IPr (1 a) or SIPr (1 b); Cp=C5H5) or (μ-Ind)(μ-Cl)Ni2(NHC) 2 (NHC=IPr (2 a) or SIPr (2 b); Ind=C7H9), which contain bridging Cp and indenyl ligands. The corresponding reaction between two equivalents of NaCp or LiInd and (μ-Cl)2Ni 2(NHC)2 (NHC=IPr or SIPr) generates unusual 17 valence electron NiI monomers of the form (η5-Cp)Ni(NHC) (NHC=IPr (3 a) or SIPr (3 b)) or (η5-Ind)Ni(NHC) (NHC=IPr (4 a) or SIPr (4 b)), which have nonlinear geometries. A combination of DFT calculations and NBO analysis suggests that the NiI monomers are more strongly stabilized by the Cp ligand than by the indenyl ligand, which is consistent with experimental results. These calculations also show that the monomers have a lone unpaired-single-electron in their valence shell, which is the reason for the nonlinear structures. At room temperature the Cp bridged dimer (μ-Cp)(μ-Cl)Ni2(NHC)2 undergoes homolytic cleavage of the Ni-Ni bond and is in equilibrium with (η5-Cp) Ni(NHC) and (μ-Cl)2Ni2(NHC)2. There is no evidence that this equilibrium occurs for (μ-Ind)(μ-Cl)Ni 2(NHC)2. DFT calculations suggest that a thermally accessible triplet state facilitates the homolytic dissociation of the Cp bridged dimers, whereas for bridging indenyl species this excited triplet state is significantly higher in energy. In stoichiometric reactions, the Ni I monomers (η5-Cp)Ni(NHC) or (η5-Ind) Ni(NHC) undergo both oxidative and reductive processes with mild reagents. Furthermore, they are rare examples of active NiI precatalysts for the Suzuki-Miyaura reaction. Complexes 1 a, 2 b, 3 a, 4 a and 4 b have been characterized by X-ray crystallography. On the nickel: The syntheses, reactivity and electronic structures of NiI monomers with terminal cyclopentadienyl (Cp) and indenyl (Ind) ligands and NiI dimers with bridging Cp and indenyl ligands are reported. NiI dimers with bridging Cp ligands undergo facile homolytic cleavage of the Ni-Ni bond and are in equilibrium with two other NiI complexes. Several of the Ni I complexes described are active precatalysts for the Suzuki-Miyaura reaction (see scheme, NHC=N-heterocyclic carbene).

Original languageEnglish
Pages (from-to)5327-5337
Number of pages11
JournalChemistry - A European Journal
Volume20
Issue number18
DOIs
Publication statusPublished - Apr 25 2014

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Nickel
Dimers
Monomers
Ligands
Lithium
Discrete Fourier transforms
Electrons
X ray crystallography
Excited states
Electronic structure
Sodium
Geometry
Temperature

Keywords

  • cross-coupling catalysis
  • electronic structure
  • metal-metal bonding
  • organometallic chemistry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Wu, J., Nova, A., Balcells, D., Brudvig, G. W., Dai, W., Guard, L. M., ... Takase, M. K. (2014). Nickel(I) monomers and dimers with cyclopentadienyl and indenyl ligands. Chemistry - A European Journal, 20(18), 5327-5337. https://doi.org/10.1002/chem.201305021

Nickel(I) monomers and dimers with cyclopentadienyl and indenyl ligands. / Wu, Jianguo; Nova, Ainara; Balcells, David; Brudvig, Gary W; Dai, Wei; Guard, Louise M.; Hazari, Nilay; Lin, Po Heng; Pokhrel, Ravi; Takase, Michael K.

In: Chemistry - A European Journal, Vol. 20, No. 18, 25.04.2014, p. 5327-5337.

Research output: Contribution to journalArticle

Wu, J, Nova, A, Balcells, D, Brudvig, GW, Dai, W, Guard, LM, Hazari, N, Lin, PH, Pokhrel, R & Takase, MK 2014, 'Nickel(I) monomers and dimers with cyclopentadienyl and indenyl ligands', Chemistry - A European Journal, vol. 20, no. 18, pp. 5327-5337. https://doi.org/10.1002/chem.201305021
Wu, Jianguo ; Nova, Ainara ; Balcells, David ; Brudvig, Gary W ; Dai, Wei ; Guard, Louise M. ; Hazari, Nilay ; Lin, Po Heng ; Pokhrel, Ravi ; Takase, Michael K. / Nickel(I) monomers and dimers with cyclopentadienyl and indenyl ligands. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 18. pp. 5327-5337.
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abstract = "The reaction of (μ-Cl)2Ni2(NHC)2 (NHC=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IPr) or 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr)) with either one equivalent of sodium cyclopentadienyl (NaCp) or lithium indenyl (LiInd) results in the formation of diamagnetic NHC supported NiI dimers of the form (μ-Cp)(μ-Cl)Ni2(NHC)2 (NHC=IPr (1 a) or SIPr (1 b); Cp=C5H5) or (μ-Ind)(μ-Cl)Ni2(NHC) 2 (NHC=IPr (2 a) or SIPr (2 b); Ind=C7H9), which contain bridging Cp and indenyl ligands. The corresponding reaction between two equivalents of NaCp or LiInd and (μ-Cl)2Ni 2(NHC)2 (NHC=IPr or SIPr) generates unusual 17 valence electron NiI monomers of the form (η5-Cp)Ni(NHC) (NHC=IPr (3 a) or SIPr (3 b)) or (η5-Ind)Ni(NHC) (NHC=IPr (4 a) or SIPr (4 b)), which have nonlinear geometries. A combination of DFT calculations and NBO analysis suggests that the NiI monomers are more strongly stabilized by the Cp ligand than by the indenyl ligand, which is consistent with experimental results. These calculations also show that the monomers have a lone unpaired-single-electron in their valence shell, which is the reason for the nonlinear structures. At room temperature the Cp bridged dimer (μ-Cp)(μ-Cl)Ni2(NHC)2 undergoes homolytic cleavage of the Ni-Ni bond and is in equilibrium with (η5-Cp) Ni(NHC) and (μ-Cl)2Ni2(NHC)2. There is no evidence that this equilibrium occurs for (μ-Ind)(μ-Cl)Ni 2(NHC)2. DFT calculations suggest that a thermally accessible triplet state facilitates the homolytic dissociation of the Cp bridged dimers, whereas for bridging indenyl species this excited triplet state is significantly higher in energy. In stoichiometric reactions, the Ni I monomers (η5-Cp)Ni(NHC) or (η5-Ind) Ni(NHC) undergo both oxidative and reductive processes with mild reagents. Furthermore, they are rare examples of active NiI precatalysts for the Suzuki-Miyaura reaction. Complexes 1 a, 2 b, 3 a, 4 a and 4 b have been characterized by X-ray crystallography. On the nickel: The syntheses, reactivity and electronic structures of NiI monomers with terminal cyclopentadienyl (Cp) and indenyl (Ind) ligands and NiI dimers with bridging Cp and indenyl ligands are reported. NiI dimers with bridging Cp ligands undergo facile homolytic cleavage of the Ni-Ni bond and are in equilibrium with two other NiI complexes. Several of the Ni I complexes described are active precatalysts for the Suzuki-Miyaura reaction (see scheme, NHC=N-heterocyclic carbene).",
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T1 - Nickel(I) monomers and dimers with cyclopentadienyl and indenyl ligands

AU - Wu, Jianguo

AU - Nova, Ainara

AU - Balcells, David

AU - Brudvig, Gary W

AU - Dai, Wei

AU - Guard, Louise M.

AU - Hazari, Nilay

AU - Lin, Po Heng

AU - Pokhrel, Ravi

AU - Takase, Michael K.

PY - 2014/4/25

Y1 - 2014/4/25

N2 - The reaction of (μ-Cl)2Ni2(NHC)2 (NHC=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IPr) or 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr)) with either one equivalent of sodium cyclopentadienyl (NaCp) or lithium indenyl (LiInd) results in the formation of diamagnetic NHC supported NiI dimers of the form (μ-Cp)(μ-Cl)Ni2(NHC)2 (NHC=IPr (1 a) or SIPr (1 b); Cp=C5H5) or (μ-Ind)(μ-Cl)Ni2(NHC) 2 (NHC=IPr (2 a) or SIPr (2 b); Ind=C7H9), which contain bridging Cp and indenyl ligands. The corresponding reaction between two equivalents of NaCp or LiInd and (μ-Cl)2Ni 2(NHC)2 (NHC=IPr or SIPr) generates unusual 17 valence electron NiI monomers of the form (η5-Cp)Ni(NHC) (NHC=IPr (3 a) or SIPr (3 b)) or (η5-Ind)Ni(NHC) (NHC=IPr (4 a) or SIPr (4 b)), which have nonlinear geometries. A combination of DFT calculations and NBO analysis suggests that the NiI monomers are more strongly stabilized by the Cp ligand than by the indenyl ligand, which is consistent with experimental results. These calculations also show that the monomers have a lone unpaired-single-electron in their valence shell, which is the reason for the nonlinear structures. At room temperature the Cp bridged dimer (μ-Cp)(μ-Cl)Ni2(NHC)2 undergoes homolytic cleavage of the Ni-Ni bond and is in equilibrium with (η5-Cp) Ni(NHC) and (μ-Cl)2Ni2(NHC)2. There is no evidence that this equilibrium occurs for (μ-Ind)(μ-Cl)Ni 2(NHC)2. DFT calculations suggest that a thermally accessible triplet state facilitates the homolytic dissociation of the Cp bridged dimers, whereas for bridging indenyl species this excited triplet state is significantly higher in energy. In stoichiometric reactions, the Ni I monomers (η5-Cp)Ni(NHC) or (η5-Ind) Ni(NHC) undergo both oxidative and reductive processes with mild reagents. Furthermore, they are rare examples of active NiI precatalysts for the Suzuki-Miyaura reaction. Complexes 1 a, 2 b, 3 a, 4 a and 4 b have been characterized by X-ray crystallography. On the nickel: The syntheses, reactivity and electronic structures of NiI monomers with terminal cyclopentadienyl (Cp) and indenyl (Ind) ligands and NiI dimers with bridging Cp and indenyl ligands are reported. NiI dimers with bridging Cp ligands undergo facile homolytic cleavage of the Ni-Ni bond and are in equilibrium with two other NiI complexes. Several of the Ni I complexes described are active precatalysts for the Suzuki-Miyaura reaction (see scheme, NHC=N-heterocyclic carbene).

AB - The reaction of (μ-Cl)2Ni2(NHC)2 (NHC=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IPr) or 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr)) with either one equivalent of sodium cyclopentadienyl (NaCp) or lithium indenyl (LiInd) results in the formation of diamagnetic NHC supported NiI dimers of the form (μ-Cp)(μ-Cl)Ni2(NHC)2 (NHC=IPr (1 a) or SIPr (1 b); Cp=C5H5) or (μ-Ind)(μ-Cl)Ni2(NHC) 2 (NHC=IPr (2 a) or SIPr (2 b); Ind=C7H9), which contain bridging Cp and indenyl ligands. The corresponding reaction between two equivalents of NaCp or LiInd and (μ-Cl)2Ni 2(NHC)2 (NHC=IPr or SIPr) generates unusual 17 valence electron NiI monomers of the form (η5-Cp)Ni(NHC) (NHC=IPr (3 a) or SIPr (3 b)) or (η5-Ind)Ni(NHC) (NHC=IPr (4 a) or SIPr (4 b)), which have nonlinear geometries. A combination of DFT calculations and NBO analysis suggests that the NiI monomers are more strongly stabilized by the Cp ligand than by the indenyl ligand, which is consistent with experimental results. These calculations also show that the monomers have a lone unpaired-single-electron in their valence shell, which is the reason for the nonlinear structures. At room temperature the Cp bridged dimer (μ-Cp)(μ-Cl)Ni2(NHC)2 undergoes homolytic cleavage of the Ni-Ni bond and is in equilibrium with (η5-Cp) Ni(NHC) and (μ-Cl)2Ni2(NHC)2. There is no evidence that this equilibrium occurs for (μ-Ind)(μ-Cl)Ni 2(NHC)2. DFT calculations suggest that a thermally accessible triplet state facilitates the homolytic dissociation of the Cp bridged dimers, whereas for bridging indenyl species this excited triplet state is significantly higher in energy. In stoichiometric reactions, the Ni I monomers (η5-Cp)Ni(NHC) or (η5-Ind) Ni(NHC) undergo both oxidative and reductive processes with mild reagents. Furthermore, they are rare examples of active NiI precatalysts for the Suzuki-Miyaura reaction. Complexes 1 a, 2 b, 3 a, 4 a and 4 b have been characterized by X-ray crystallography. On the nickel: The syntheses, reactivity and electronic structures of NiI monomers with terminal cyclopentadienyl (Cp) and indenyl (Ind) ligands and NiI dimers with bridging Cp and indenyl ligands are reported. NiI dimers with bridging Cp ligands undergo facile homolytic cleavage of the Ni-Ni bond and are in equilibrium with two other NiI complexes. Several of the Ni I complexes described are active precatalysts for the Suzuki-Miyaura reaction (see scheme, NHC=N-heterocyclic carbene).

KW - cross-coupling catalysis

KW - electronic structure

KW - metal-metal bonding

KW - organometallic chemistry

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