Mason, Chris2013-11-072013-11-0720102010Source: Masters Abstracts International, Volume: 49-02, page: 1187.http://hdl.handle.net/10393/28515http://dx.doi.org/10.20381/ruor-19308Combination of the potassium salt of the triazenide anion (R)NNN(R) - with CrCl2(THF)2 leads to the formation of dimeric complexes {Cr[mu,eta,eta'-bis-1,3-(2',5'-diisopropylphenyl) triazenide]2}2(2.1), [Cr(mu,eta,eta')-1,3-diphenyltriazenide) 2]2 (2.2), {Cr[mu,eta,eta')-bis-1,3-(2'-methoxyphenyl)triazenide] 2}2 (2.3) which are paddlewheel type structures featuring bridging triazenide anions. These complexes led to very low activity for the polymerization and oligomerization of ethylene upon activation with known activators MAO, TIBAO. Combination of the potassium salt of the triazenide anion with CrCl 3(THF)3 leads to the formation of mononuclear complexes [bis-1,3-(2',5'-diisopropylphenyl) triazenide]Cr(THF)2Cl2 (2.5) and [bis-1,3-(2'-methoxyphenyl) triazenide]Cr(THF)2Cl2 (2.6). These complexes showed high activity for the non-selective oligomerization of ethylene, fitting a Schulz-Flory distribution. Reduction of these complexes lead to the dinuclear CrII species {[bis-1,3-(2',5'-diisopropylphenyl)triazenide]Cr(THF)(muCl)} 2(2.7), but did not lead to the target Cr1 complexes as ligand salts were isolated upon further reduction. One pot reaction of ZrCl4 with 2 equivalents of mono-pyrrole based ligands and 4 equivalents of AlR3 leads to the formation of zirconocene type structures (eta)5[2,5-Me2C 4H2N{AlCl2Et}]2ZrCl2 ( 3.1), (eta5[2,5-Me2C4H 2N{AlClMe2}])2ZrClMe (3.2), (eta 5[2,5-Me2C4H2N{AlClMe2}]) 2ZrCl2 (3.3), (eta5[C 4H4N{AlClMe2}])2ZrMe2 ( 3.4). These ZrIV complexes produced lower than expected activity for polymerization of ethylene when activated by MAO, as compared to their Cp analogues. When dipyrrole ligands were combined with ZrCl4 and 4 equivalents of AlR3 in one pot, formation of ZrIII compounds were observed. Octameric ([{Ph2C(C4H3N) 2}Zr2]4(mu-Cl)16) [mu-Cl] 2AlCl2)4 (3.5) provides a Zr III complex unlike any other observed in literature. Reduction was performed from Al(Me)3 in this case, however coordination of Al in the structure is unlike the previous 3.1,3.2,3.3,3.4. The formation of ([AlEtCl{mu-Cl}2][{C4H 4N}2AlClEt]Zr2(mu-Cl)4)2 · 4 (C7H8) (3.7) has many interesting features. The Zr-Zr distance of 3.045(2)A is the shortest yet observed for Zr. Additionally, the dipyrrole starting material was cleaved during the reaction to basic pyrrole, which suggests insight into the mechanism of formation of 3.5 and suggests the possibility of in situ Zr II formation.123 p.enChemistry, Inorganic.Chemistry, Organic.Thesis