Skip to main content
SpringerLink
Log in

Molecular Rare Earth Hydride Clusters

  • Chapter
  • First Online:
Recent Development in Clusters of Rare Earths and Actinides: Chemistry and Materials

Part of the book series: Structure and Bonding ((STRUCTURE,volume 173))

Abstract

This chapter describes the synthesis, structure, and reactivity of molecular rare earth hydride clusters consisting of the dihydride species “(L)LnH2” bearing one anionic supporting ligand per metal. Generally, hydrogenolysis of the dialkyl precursors [(L)LnR2] with H2 easily leads to formation of polynuclear rare earth hydride clusters through self-assembly of the resulting dihydride species. The molecular structure and reactivity of the hydride clusters are significantly influenced by both the bulkiness of the ancillary ligands and the size of the metal ions. Unique reactivities are observed with various substrates, including CO, CO2, H2, and unsaturated C–C and C–N bonds, because of the synergistic effects of the multiple metal-hydride sites.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Evans WJ, Atwood JL et al (1982) Organolanthanide hydride chemistry. 1. Synthesis and X-ray crystallographic characterization of dimeric organolanthanide and organoyttrium hydride complexes. J Am Chem Soc 104:2008–2014

    Article  CAS  Google Scholar 

  2. Marks TJ et al (1985) Highly reactive organolanthanides. Systematic routes to and olefin chemistry of early and late bis(pentamethylcyclopentadienyl) 4f hydrocarbyl and hydride complexes. J Am Chem Soc 107:8091–8103

    Article  Google Scholar 

  3. Bercaw JE et al (1987) σ-Bond metathesis for C-H bonds of hydrocarbons and Sc-R (R = H, alkyl, aryl) bonds of permethylscandocene derivatives. Evidence for noninvolvement of the π system in electrophilic activation of aromatic and vinylic C-H bonds. J Am Chem Soc 109:203–219

    Article  Google Scholar 

  4. Den Haan KH, Wielstra Y, Teuben JH (1987) Reaction of yttrium-carbon bonds with active hydrogen-containing molecules. A useful synthetic method for permethylyttrocene derivatives. Organometallics 6:2053–2060

    Article  Google Scholar 

  5. Nishiura M, Hou Z (2011) Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls. Nat Chem 2:257–268

    Article  Google Scholar 

  6. Fegler W, Okuda J et al (2015) Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments. Angew Chem Int Ed 54:1724–1736

    Article  CAS  Google Scholar 

  7. Nishiura M, Hou Z (2010) Half-sandwich rare earth metal complexes as novel catalysts for olefin polymerization and other chemical transformations. Bull Chem Soc Jpn 83:595–608

    Article  CAS  Google Scholar 

  8. Nishiura M, Guo F, Hou Z (2015) Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation. Acc Chem Res 48:2209–2220

    Article  CAS  Google Scholar 

  9. Hou Z, Nishiura M, Shima T (2007) Synthesis and reactions of polynuclear polyhydrido rare earth metal complexes containing “(C5Me4SiMe3)LnH2” units: a new frontier in rare earth metal hydride chemistry. Eur J Inorg Chem 2007:2535–2545

    Article  Google Scholar 

  10. Nishiura M, Hou Z et al (2011) Synthesis and structures of the C5Me4SiMe3-supported polyhydride complexes over the full size range of the rare earth series. Chem Eur J 17:5033–5044

    Article  CAS  Google Scholar 

  11. Cui D, Tardif O, Hou Z (2004) Tetranuclear rare earth metal polyhydrido complexes composed of “(C5Me4SiMe3)LnH2” units. Unique reactivities toward unsaturated C-C, C-N, and C-O bonds. J Am Chem Soc 126:1312–1313

    Article  CAS  Google Scholar 

  12. Tardif O, Nishiura M, Hou Z (2003) Isolation and structural characterization of a polyhydrido lanthanide cluster complex consisting of “(C5Me4SiMe3)LuH2” units. Organometallics 22:1171–1173

    Article  CAS  Google Scholar 

  13. Hultzsch K, Spaniol TP, Okuda J (1999) Half-sandwich alkyl and hydrido complexes of yttrium: convenient synthesis and polymerization catalysis of polar monomers. Angew Chem Int Ed 38:227–230

    Article  CAS  Google Scholar 

  14. Hou Z, Wakatsuki Y et al (2001) (Pentamethylcyclopentadienyl)samarium(II) alkyl complex with the neutral “C5Me5K” ligand: a precursor to the first dihydrido lanthanide(III) complex and a precursor for hydrosilylation of olefins. J Am Chem Soc 123:9216–9217

    Article  CAS  Google Scholar 

  15. van der Heijden H, Schaverien CJ, Orpen AG et al (1989) Neutral monocyclopentadienyllutetium alkyls: in search of steric unsaturation. Organometallics 8:1459–1467

    Article  Google Scholar 

  16. Shima T, Nishiura M, Hou Z (2011) Tetra-, penta-, and hexanuclear yttrium hydride clusters from half-sandwich bis(aminobenzyl) complexes containing various cyclopentadienyl ligands. Organometallics 30:2513–2524

    Article  CAS  Google Scholar 

  17. Shima T, Hou Z (2008) Activation and dehydrogenative silylation of the C–H bonds of phosphine-coordinated ruthenium in Lu/Ru heteromultimetallic hydride complexes. Chem Lett 37:298–299

    Article  CAS  Google Scholar 

  18. Shima T, Hou Z (2009) Rare earth/d-transition metal heteromultimetallic polyhydride complexes based on half-sandwich rare earth moieties. Organometallics 28:2244–2252

    Article  CAS  Google Scholar 

  19. Cheng J, Ferguson MJ, Takats J (2010) Synthesis and reaction of [(TpiPr2)LnH2]3 (Ln = Y, Lu) with CO: trinuclear cluster-bound propenolate en route to selective formation of propene. J Am Chem Soc 132:2–3

    Article  CAS  Google Scholar 

  20. Cheng J, Takats J et al (2008) Scorpionate-supported dialkyl and dihydride lanthanide complexes: ligand- and solvent-dependent cluster hydride formation. Angew Chem Int Ed 47:4910–4913

    Article  CAS  Google Scholar 

  21. Johnson KRD, Kamenz BL, Hayes PG (2014) Bis(pyrazolyl)carbazole as a versatile ligand for supporting lutetium alkyl and hydride complexes. Organometallics 33:3005–3011

    Article  CAS  Google Scholar 

  22. Ohashi M, Okuda J et al (2008) Rare-earth metal alkyl and hydride complexes stabilized by a cyclen-derived [NNNN] macrocyclic ancillary ligand. J Am Chem Soc 130:6920–6921

    Article  CAS  Google Scholar 

  23. Abinet E, Okuda J et al (2011) Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: synthesis, structure, and reactivity toward biomass-derived furanics. Chem Eur J 17:15014–15026

    Article  CAS  Google Scholar 

  24. Martin D, Okuda J et al (2013) Hydrido and allyl/hydrido complexes of early lanthanides supported by an NNNN-type macrocyclic ligand. Eur J Inorg Chem 2013:3987–3992

    Article  CAS  Google Scholar 

  25. Cheng J, Shima T, Hou Z (2011) Rare-earth polyhydride complexes bearing bis(phosphinophenyl)amido pincer ligands. Angew Chem Int Ed 50:1857–1860

    Article  CAS  Google Scholar 

  26. Wylie WNO, Hou Z et al (2014) PNP-ligated heterometallic rare-earth/ruthenium hydride complexes bearing phosphinophenyl and phosphinomethyl bridging ligands. Organometallics 33:1030–1043

    Article  Google Scholar 

  27. Lyubov DM, Kempe R, Trifonov AA et al (2008) Selective assembly of trinuclear rare-earth alkyl hydrido clusters supported by amidopyridinate ligands. Organometallics 27:2905–2907

    Article  CAS  Google Scholar 

  28. Lyubov DM, Trifonov AA et al (2014) Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C–Si bond activation and catalytic activity in ethylene polymerization. Dalton Trans 43:14450–14460

    Article  CAS  Google Scholar 

  29. Cheng J, Hou Z et al (2012) Binuclear rare-earth polyhydride complexes bearing both terminal and bridging hydride ligands. Chem Sci 3:2230–2233

    Article  CAS  Google Scholar 

  30. Li X, Baldamus J, Hou Z et al (2006) Cationic rare-earth polyhydrido complexes: synthesis, structure, and catalytic activity for the cis 1,4-selective polymerization of 1,3-cyclohexadiene. Angew Chem Int Ed 45:8184–8188

    Article  CAS  Google Scholar 

  31. Ferrence GM, McDonald R, Takats J (1999) Stabilization of a discrete lanthanide(II) hydrido complex by a bulky hydrotris(pyrazolyl)borate ligand. Angew Chem Int Ed 38:2233–2237

    Article  CAS  Google Scholar 

  32. Shima T, Hou Z (2006) Hydrogenation of carbon monoxide by tetranuclear rare earth metal polyhydrido complexes. Selective formation of ethylene and isolation of well-defined polyoxo rare earth metal clusters. J Am Chem Soc 128:8124–8125

    Article  CAS  Google Scholar 

  33. Tardif O, Hashizume D, Hou Z (2004) Hydrogenation of carbon dioxide and aryl isocyanates by a tetranuclear tetrahydrido yttrium complex. Isolation, structures, and CO2-insertion reactions of methylene diolate and 3-oxo yttrium complexes. J Am Chem Soc 126:8080–8081

    Article  CAS  Google Scholar 

  34. Cui D, Nishiura M, Hou Z (2005) Lanthanide–imido complexes and their reactions with benzonitrile. Angew Chem Int Ed 44:959–961

    Article  CAS  Google Scholar 

  35. St. Clair MA, Santarsiero BD, Bercaw JE (1989) Addition of scandium-hydrogen, scandium-carbon, and scandium-nitrogen bonds to coordinated carbon monoxide. Structure of a methylscandoxycarbene derivative of cobalt. Organometallics 8:17–22

    Article  CAS  Google Scholar 

  36. Takenaka Y, Shima T, Hou Z et al (2009) Reduction of transition-metal-coordinated carbon monoxide by a rare-earth hydride cluster: isolation of well-defined heteromultimetallic oxycarbene, oxymethyl, carbene, and methyl complexes. Angew Chem Int Ed 48:7888–7891

    Article  CAS  Google Scholar 

  37. Shima T, Luo Y, Hou Z et al (2011) Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals. Nat Chem 3:814–820

    Article  CAS  Google Scholar 

  38. Shima T, Hou Z (2013) Heterometallic polyhydride complexes containing yttrium hydrides with different Cp ligands: synthesis, structure, and hydrogen-uptake/release properties. Chem Eur J 19:3458–3466

    Article  CAS  Google Scholar 

  39. Lyubov DM, Kempe R, Trifonov AA et al (2011) Selective protonation of the Y–C bond in trinuclear yttrium alkyl-hydrido clusters and formation of the cationic polyhydrido core. Chem Eur J 17:3824–3826

    Article  CAS  Google Scholar 

  40. Cheng J, Hou Z (2012) Cationic terminal hydrido rare earth complexes bearing an amidinate ancillary ligand. Chem Commun 48:814–816

    Article  CAS  Google Scholar 

  41. Fegler W, Venugopal A, Okuda J et al (2013) Reversible dihydrogen activation in cationic rare-earth-metal polyhydride complexes. Angew Chem Int Ed 52:7976–7980

    Article  CAS  Google Scholar 

  42. Shima T, Hu S, Hou Z et al (2013) Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex. Science 340:1549–1552

    Article  CAS  Google Scholar 

  43. Hu S, Shima T, Hou Z (2014) Carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride. Nature 512:413–415

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Organometallic Chemistry Laboratory, RIKEN Center for Sustainable Resource Science, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan

    Takanori Shima & Zhaomin Hou

Authors
  1. Takanori Shima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhaomin Hou
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zhaomin Hou .

Editor information

Editors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona, USA

    Zhiping Zheng

Rights and permissions

Reprints and permissions

Copyright information

© 2016 Springer International Publishing Switzerland

About this chapter

Cite this chapter

Shima, T., Hou, Z. (2016). Molecular Rare Earth Hydride Clusters. In: Zheng, Z. (eds) Recent Development in Clusters of Rare Earths and Actinides: Chemistry and Materials. Structure and Bonding, vol 173. Springer, Berlin, Heidelberg. https://doi.org/10.1007/430_2016_7

Download citation

Publish with us

Policies and ethics

Search

Navigation