Ni(COD)(DQ)

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Ni(COD)(DQ)
Solid Ni(COD)(DQ).jpg
Ni(COD)(DQ) is red in solid crystalline form
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C10H12O2.C8H12.Ni/c1-5-6(2)10(12)8(4)7(3)9(5)11;1-2-4-6-8-7-5-3-1;/h1-4H3;1-2,7-8H,3-6H2;
    Key: KMQIRZWEKVPSAZ-UHFFFAOYSA-N
  • CC1=C(C(=O)C(=C(C1=O)C)C)C.C1CC=CCCC=C1.[Ni]
Properties
C18H24NiO2
Molar mass 331.081 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Ni(COD)(DQ), formally known as bis(1,5-cyclooctadiene)(duroquinone)nickel(0), is an organonickel compound with the empirical formula NiC18H24O2. [1] It is a coordination complex composed of a nickel(0) center ligated by a 1,5-cyclooctadiene (COD) and a duroquinone (DQ) ligand. The compound is of interest in organometallic chemistry because despite being an 18-electron complex, Ni(COD)(DQ) exhibits reactivity not found in more common Ni(0) sources and serves as a useful precursor in homogeneous catalysis and nickel-mediated cross-coupling reactions. [2] [3]

Contents

History

The first synthetic route to Ni(COD)(DQ) proposed by Schrauzer and coworkers First synthesis of Ni(COD)(DQ).png
The first synthetic route to Ni(COD)(DQ) proposed by Schrauzer and coworkers

The complex was first reported by Schrauzer in 1962 and synthesized by refluxing Ni(CO)4, duroquinone, and cyclooctadiene in dry dichloromethane (85% yield). [4] After the discovery of ferrocene in the early 1950s, [5] Schrauzer aimed to develop new, stable, transition metal–olefin sandwich complexes. [4] Decades later, Ni(COD)(DQ) gained renewed attention when Keary Engle at Scripps Research identified it in 2020 as a highly effective Ni(0) precatalyst. Ni(COD)(DQ) was found to be an isoelectronic and isostructural, but air and moisture stable alternative to Bis(cyclooctadiene)nickel(0) (Ni(COD)2)—another prominent Ni(0) pre-catalyst. [2]

Structure and Bonding

The reported structure of Ni(COD)(DQ) Ni(COD)(DQ).png
The reported structure of Ni(COD)(DQ)

Ni(COD)(DQ) is a tetrahedral complex where the nickel(0) center is coordinated by one COD ligand and one duroquinone ligand. The DQ ligand is a strong π-acceptor and helps stabilize the low-valent nickel center through π-backbonding. The electron-rich nature of the nickel(0) center and the labile coordination environment make the complex a valuable source of Ni(0) for catalytic transformations. [3] [2]

Synthesis

Ni(COD)(DQ) is typically synthesized by the reaction of Ni(COD)2 with duroquinone (DQ) under inert atmosphere conditions:

Ni(COD)2 + DQ → Ni(COD)(DQ) + COD

More recently developed alternative syntheses of Ni(COD)(DQ) Synthesis of Ni(COD)(DQ).png
More recently developed alternative syntheses of Ni(COD)(DQ)

This reaction proceeds readily at mild temperature and provides Ni(COD)(DQ) in good yields. Alternatively, Ni(COD)(DQ) can be prepared from various air-stable Ni(II) sources including Ni(acac)2 or NiCl2(pyridine)4 with DIBAL-H or sodium as the reductant respectively. [2]

Applications

Ni(COD)(DQ) has proved useful in a variety of catalytic reactions as an alternative to Ni(COD)2 as it is air and moisture stable and has demonstrated greater thermal stability. [6] These features allow for its use in catalytic reactions without the need for rigorous inert atmosphere techniques, making it attractive for bench-scale experimentation. Ni(COD)(DQ) serves as a competent Ni(0) precatalyst for a wide variety of nickel-catalyzed transformations:

Recent catalytic applications involving Ni(COD)(DQ) Recent Applications.png
Recent catalytic applications involving Ni(COD)(DQ)

References

  1. ↑ Sigma Aldrich
  2. 1 2 3 4 Tran, V. T.; Li, Z.; Apolinar, O.; Derosa, J.; Joannou, M. V.; Wisniewski, S. R.; Eastgate, M. D.; Engle, K. M. Ni(COD)(DQ): An Air-Stable 18-Electron Nickel(0)–Olefin Precatalyst. Angew. Chem. Int. Ed.2020, 59, 7409–7413 DOI:10.1002/anie.202000124.
  3. 1 2 Glick, M. D.; Dahl, L. F. Structure of and bonding in I,5-cyclooctadiene-duroquinone nickel. Journal of Organometallic Chemistry1965, 3, 200–221 DOI: 10.1016/S0022-328X(00)87502-6.
  4. 1 2 Schrauzer, G.N. and H. Thyret, Neuartige, Sandwich“-Verbindungen des Nickel(0). Zur Kenntnis von Durodhinon-Nickel(0)-Komplexen mit cyclischen Dienen. Zeitschrift für Naturforschung B,1962. 17(2): p. 73-76.
  5. ↑ Kauffman, G.B., The discovery of ferrocene, the first sandwich compound. J. Chem. Ed.,1983. 60(3): p. 185 DOI: 10.1021/ed060p185.
  6. 1 2 3 Tran, V.T., et al., Structurally Diverse Bench-Stable Nickel(0) Pre-Catalysts: A Practical Toolkit for In Situ Ligation Protocols. Angew. Chem. Int. Ed.,2023. 62(9): p. e202211794. 10.1002/anie.202211794.
  7. ↑ You, T. and J. Li, Ni(cod)(duroquinone)-Catalyzed C–N Cross-Coupling for the Synthesis of N,N-Diarylsulfonamides. Organic Letters,2022. 24(36): p. 6642-6646. DOI:10.1021/acs.orglett.2c02670
  8. ↑ Noda, N., et al., The Use of Ni(cod)(dq) (COD: 1,5-Cyclooctadiene; DQ: Duroquinone) for the Dehalogenative Coupling Polycondensation to π-Conjugated Polyarylenes. Process Research & Development,2025. 29(3): p. 932-937
  9. ↑ Tyerman, S., C.M. Robertson, and J.A. Murphy, Radical coupling of aryl halides to arenes facilitated by Ni(COD)(DQ) and other nickel sources. Organic & Biomolecular Chemistry,2024. 22(5): p. 1023-1026.
  10. ↑ Li, Y., et al., Highly selective synthesis of all-carbon tetrasubstituted alkenes by deoxygenative alkenylation of carboxylic acids. Nature Communications,2022. 13(1): p. 10.
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