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Synthesis, structures and reactions of hydrotris(pyrazolyl)borate complexes of divalent and trivalent lanthanides Open Access


Other title
Bis-alkynide Complexes
Head-to Head Coupling
Dimerization of Terminal Alkynes
Dihydride Complexes
Dialkyl Complexes
Hydrotris(pyrazolyl)borate Ligands
Tribenzyl Complexes
Type of item
Degree grantor
University of Alberta
Author or creator
Saliu, Kuburat Olubanke
Supervisor and department
Examining committee member and department
Roderick E. Wasylishen (Chemistry)
Josef Takats (Chemistry)
Jonathan G. C. Veinot (Chemistry)
Suzanne M. Kresta (Chemical and Materials Engineering)
David J. Berg (Chemistry, University of Victoria)
Steven H. Bergens (Chemistry)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
The synthesis and reactions of hydrotris(pyrazolyl)borate, (TpR,R′) supported ytterbium(II) borohydride and lanthanide(III) dialkyl (Ln = Yb, Lu) complexes were investigated. The lanthanide(III) dialkyl complexes were found to undergo both hydrogenolysis reaction and protonolysis reaction with terminal alkynes. Reaction of [(TptBu,Me)YbH]2 (1) with NH3BH3 and (TptBu,Me)YbI(THF) (2) with NaBH4 afforded the corresponding mono-ligand complexes, (TptBu,Me)Yb(BH4) (3) and (TptBu,Me)Yb(BH4)(THF) (4), respectively. Compounds 3 and 4 represent rare examples of lanthanide(II) tetrahydroborate complexes. IR spectroscopy data, in the B-H stretching region are consistent with the κ3-BH4 bonding mode found in the solid state of compound 4 and the corresponding deuterium labelled BD4 analogue of 4 shows the expected IR isotope shifts. Mono-ligand lanthanide dialkyl complexes, (TpR,R′)Ln(CH2SiMe2Rʺ)2(THF)0/1 (5-9) were synthesized from the homoleptic Ln(CH2SiMe2Rʺ)3(THF)2 (Ln = Yb, Lu; Rʺ = Me, Ph) complexes by two alternative and complementary methods: alkyl abstraction with the thallium salts of the ligands, TlTpR,Rʹ and protonolysis using the acid form of the ligands, HTpR,Rʹ. Hydrogenolysis of the dialkyl complexes (TpMe2)Ln(CH2SiMe3)2(THF) (7a, Yb; 8a, Lu) afforded the corresponding tetranuclear hydride complexes, [(TpMe2)LnH2]4 (11, Yb; 12, Lu). Similarly, hydrogenolysis of (Tp)Yb(CH2SiMe3)2(THF) (9) afforded the hexanuclear hydride [(Tp)YbH2]6 (13). When treated with a variety of terminal alkynes, the dialkyl complexes, (TpR,Me)Ln(CH2SiMe3)2(THF) (14a, Y; 8a, Lu), gave the corresponding bis-alkynide complexes, “(TpR,Me)Ln(CCRʺ)2” (15-27). The structures of the complexes depend on the steric size of both the alkyne substituents and the substituent on position 3 of the pyrazolyl ring. Except for the bulkiest substituents, the compounds are dimeric with two asymmetric μ2-alkynide bridging groups and a coupled alkynide unit bridging the two lanthanide centers via an unusual enyne bonding motif. The synthesis of Lu(CH2Ph-4-R)3(THF)3 (R = H, 28a; R = Me, 28b) was achieved by salt metathesis reactions between KCH2Ph-4-R and LuCl3. Variable temperature NMR studies in THF shows that the formation of these complexes is accompanied by a small amount of the anionic ʹateʹ K[Lu(CH2PH-4-R)4(THF)n] (30) complexes, which can be prepared independently by reaction of pure Lu(CH2Ph-4-R)3(THF)3 with one equiv. of KCH2Ph-4-R. One of the coordinated THF of 28a could be removed by trituration with toluene to give Lu(CH2Ph-4-R)3(THF)2 (29a). Protonolysis reaction with HTpR,Rʹ afforded the corresponding dibenzyl complexes, (TpR,R’)Ln(CH2Ph-4-R)2(THF)n (31-33). X-ray crystal structures of complex 4, the dialkyl complexes 5b, 6b, 7 and 8; dihydride complexes 11, 12 and 13; bis-alkynide complexes 15, 16, 17, 21, 22 and 24 as well as the tribenzyl compounds 28a and 29a and dibenzyl complexes 31-33 were determined. The solution behaviour, solid state structures and structural diversity of these complexes are discussed.
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