Register      Login
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE (Open Access)

Extremely bulky β-diketiminate complexes of calcium(ii) and ytterbium(ii)

Brant Maitland A , Andreas Stasch A and Cameron Jones https://orcid.org/0000-0002-7269-1045 A *
+ Author Affiliations
- Author Affiliations

A School of Chemistry, PO Box 23, Monash University, Melbourne, Vic., 3800, Australia.

* Correspondence to: cameron.jones@monash.edu

Handling Editor: George Koutsantonis

Australian Journal of Chemistry 75(9) 543-548 https://doi.org/10.1071/CH21283
Submitted: 1 November 2021  Accepted: 13 December 2021   Published: 18 February 2022

© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)

Abstract

The potassium salt of an extremely bulky β-diketiminate, [K(Ar*Nacnac)] (Ar*Nacnac, [(Ar*NCMe)2CH]; Ar*, C6H2Me{C(H)Ph2}2-4,2,6) was reacted with either CaI2 or YbI2(THF)2, which afforded [(Ar*Nacnac)MI] (M = Ca or Yb). These are the first examples of structurally characterised, donor solvent-free, N-arene substituted β-diketiminato calcium and ytterbium complexes that incorporate a terminal iodide ligand. Reduction of [(Ar*Nacnac)CaI] with sodium metal gave a complex product mixture, from which a few crystals of the β-diketiminate C–H activated product, [{Ca(μ-Ar*Nacnac-H)}2], were obtained and crystallographically characterised. In an attempt to form a terminal ytterbium hydride compound, treatment of [(Ar*Nacnac)YbI] with K[HBEt3] gave a good yield of the contact ion pair compound [(Ar*Nacnac)Yb(HBEt3)].

Keywords: β‐diketiminate, bulky ligand, calcium, C–H activation, metal hydrides, metal–metal bonding, reduction, ytterbium.


References

[1]  (a) L Bourget-Merle, MF Lappert, JR Severin, Chem Rev 2002, 102, 3031.
         | Crossref | GoogleScholarGoogle Scholar | 12222981PubMed |
      (b) Y-C Tsai, Coord Chem Rev 2012, 256, 722.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) RL Webster, Dalton Trans 2017, 46, 4483.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) M Asay, C Jones, M Driess, Chem Rev 2011, 111, 354.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) C Camp, J Arnold, Dalton Trans 2016, 45, 14462.
         | Crossref | GoogleScholarGoogle Scholar |

[2]  S Green, C Jones, A Stasch, Science 2007, 318, 1754.
         | Crossref | GoogleScholarGoogle Scholar | 17991827PubMed |

[3]  (a) C Jones, Nat Rev Chem 2017, 1, 0059.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) A Stasch, C Jones, Dalton Trans 2011, 40, 5659.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) C Jones, Commun Chem 2020, 3, 159.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) C Jones, A Stasch, Top Organomet Chem 2013, 45, 73.
         | Crossref | GoogleScholarGoogle Scholar |

[4]  SJ Bonyhady, D Collis, N Holzmann, AJ Edwards, RO Piltz, G Frenking, A Stasch, C Jones, Nat Commun 2018, 9, 3079.
         | Crossref | GoogleScholarGoogle Scholar | 30082681PubMed |

[5]  K Yuvaraj, I Iskander, DDL Jones, L Maron, C Jones, Chem Sci 2020, 11, 3516.
         | Crossref | GoogleScholarGoogle Scholar | 34109023PubMed |

[6]  TX Gentner, B Rösch, G Ballmann, J Langer, H Elsen, S Harder, Angew Chem, Int Ed 2019, 58, 607.
         | Crossref | GoogleScholarGoogle Scholar |

[7]  (a) B Rösch, TX Gentner, J Eyselein, J Langer, H Elsen, S Harder, Nature 2021, 592, 717.
         | Crossref | GoogleScholarGoogle Scholar | 33911274PubMed |
      (b) C Jones, Nature 2021, 592, 687.
         | Crossref | GoogleScholarGoogle Scholar |

[8]  B Rösch, TX Gentner, J Langer, G Färber, J Eyselein, L Zhao, C Ding, G Frenking, S Harder, Science 2021, 371, 1125.
         | Crossref | GoogleScholarGoogle Scholar | 33707259PubMed |

[9]  (a) SP Green, C Jones, A Stasch, Angew Chem Int Ed 2008, 47, 9079.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) R Lalrempuia, CE Kefalidis, SJ Bonyhady, B Schwarze, L Maron, A Stasch, C Jones, J Am Chem Soc 2015, 137, 8944.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) CN deBruin-Dickason, CA Rosengarten, GB Deacon, C Jones, Chem Commun 2021, 57, 1599.
         | Crossref | GoogleScholarGoogle Scholar |

[10]  (a) ASS Wilson, MS Hill, MF Mahon, C Dinoi, L Maron, Science 2017, 358, 1168.
         | Crossref | GoogleScholarGoogle Scholar | 29191904PubMed |
      (b) S Harder, J Brettar, Angew Chem Int Ed 2006, 45, 3474.
         | Crossref | GoogleScholarGoogle Scholar |

[11]     (a) See, for example: In: S Harder, editor. Alkaline-Earth Metal Compounds: Oddities and Applications. Heidelberg: Springer; 2013
      (b) MS Hill, DJ Liptrot, Chem Soc Rev 2016, 45, 972.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) B Mukherjee, D Scuhknecht, J Okuda, Angew Chem Int Ed 2018, 57, 9590.
         | Crossref | GoogleScholarGoogle Scholar |

[12]  B Rosch, TX Gentner, H Elsen, CA Fischer, J Langer, M Wiesinger, S Harder, Angew Chem Int Ed 2019, 58, 5396.
         | Crossref | GoogleScholarGoogle Scholar |

[13]  M Arrowsmith, B Maitland, G Kociok-Kohn, A Stasch, C Jones, MS Hill, Inorg Chem 2014, 53, 10543.
         | Crossref | GoogleScholarGoogle Scholar | 25203490PubMed |

[14]  RD Shannon, Acta Crystallogr 1976, A32, 751.
         | Crossref | GoogleScholarGoogle Scholar |

[15]  C Ruspic, J Spielmann, S Harder, Inorg Chem 2007, 46, 5320.
         | Crossref | GoogleScholarGoogle Scholar | 17530842PubMed |

[16]  GG Skvortsov, GK Fukin, AV Cherkasov, TA Kovylina, AA Trifonov, Inorg Chem Acta 2020, 508, 119623.
         | Crossref | GoogleScholarGoogle Scholar |

[17]  SJ Bonyhady, C Jones, S Nembenna, A Stasch, AJ Edwards, GJ McIntyre, Chem Eur J 2010, 16, 938.
         | Crossref | GoogleScholarGoogle Scholar | 19950340PubMed |

[18]  C Jones, S Nembenna, A Stasch, J Chem Crystallogr 2011, 41, 1490.
         | Crossref | GoogleScholarGoogle Scholar |

[19]  R Fischer, M Gärtner, H Görls, M Westerhausen, Organometallics 2006, 25, 3496.
         | Crossref | GoogleScholarGoogle Scholar |

[20]  For examples of hydride bridged β-diketiminato ytterbium(II) compounds see ref. [15], and GM Richardson, I Douair, SA Cameron, J Bracegirdle, RA Keyzers, MS Hill, L Maron, MD Anker, Nat Commun 2021, 12, 3147.
         | Crossref | GoogleScholarGoogle Scholar | 34035284PubMed |

[21]  SP Sarish, A Jana, HW Roesky, T Schulz, M John, D Stalke, Inorg Chem 2010, 49, 3816.
         | Crossref | GoogleScholarGoogle Scholar |

[22]  TM McPhillips, SE McPhillips, HJ Chiu, AE Cohen, AM Deacon, PJ Ellis, E Garman, A Gonzalez, NK Sauter, RP Phizackerley, SM Soltis, P Kuhn, J Synchrotron Rad 2002, 9, 401.
         | Crossref | GoogleScholarGoogle Scholar |

[23]  W Kabsch, J Appl Cryst 1993, 26, 795.
         | Crossref | GoogleScholarGoogle Scholar |

[24]  Sheldrick GM. SHELX-16. University of Göttingen; 2016.