| C,C'-Linked dicarbollide species [Me3NH][7,8-CH 2OCH2-7,8-C2B9H10] and 1-(1-indenyl)-1,2-carborane were synthesized. Their applications in rare earth chemistry were studied and discussed in this thesis.;[Me3NH][7,8-CH2OCH2-7,8-C2B 9H10] was prepared by the deboration reaction of (CH 2OCH2)C2B10H10. Ln(CH 2C6H4-o-NMe2) 3 (Ln = Y, Gd, Er) reacted with this ligand to form half-sandwich metallacarboranes [eta5 -(CH2OCH2)C2B 9H9]Ln[sigma:sigma-(CH2C6H 4-o-NMe2)](THF)2. Unsaturated polar organic substrates, such as isocyanide, isothiocyanate, and isocynate can insert into the M-C bond to form mono-insertion complexes or di-insertion complexes depending on the steric factor of the substrate.;[eta5:sigma-(C9H6)C2B 10H10]Ln[sigma:sigma-(CH2C6H 4-o-NMe2)](THF)2 and [sigma:eta 5-O(CH2)2C2B9H9]Y[sigma:sigma-(CH 2C6H4-o-NMe2)](THF)2 were studied. Complex [sigma:eta5-O(CH2) 2C2B9H9]Y[sigma:sigma-(CH 2C6H4-o-NMe2)](THF) 2 reacted with various guanidines to give the corresponding guanidinato products.;Complex [(1-C9H6)(C2B9H 10)]Y(DME)2 was synthesized and structurally characterized from the reaction of [Me3NH][(C9H7)C2B9H11] with Y(CH2-o-NMe2-C6H 4)3 in DME. Its reactivity was examined. It reacted with diphenylketone, diphenylketene, di(2-pyridyl)ketone and other unsaturated organic compounds to afford mono-insertion products with similar structures.;1-(1-Indenyl)-1,2-carborane was synthesized from the reaction of indene epoxide with dilithium salt of carborane. Reaction of this ligand with Ln(CH 2C6H4-o-NMe2) 3 (Ln = Y, Gd, Er, Dy) led to the formation of [eta5:sigma-(C 9H6)C2B10H10]Ln[sigma:sigma-(CH 2C6H4-o-NMe2)](THF) 2 (Ln= Y, Gd, Er, Dy). The metal-carbon sigma bond in these complexes was reactive toward unsaturated polar organic substrates, such as carbodiimide, isocyanide, isothiocyanate, and isocynate. They reacted with R-N=C=N-R (R= TMS, tBu) to form mono-insertion products. The metal-cage carbon sigma bond in the mono-insertion product was also active toward unsaturated polar organic substrates to form di-insertion complexes. And the indenyl-carboranyl gadolinium complex can be protonated to give ionic species. |
