Symmetric N,N′-dialkyl-2-amino-4-imino-pent-2-enes (nacnacRH) can be prepared in high yields in a simple one-pot reaction from acetylacetone and 2 equiv. of amine. Optimized conditions require the azeotropic removal of water, use of a minimum amount of solvent, and of 1 equiv. of acid. Either para-toluenesulfonic acid, hydrochloric acid, or a mixture of both can be employed, with the latter being most advantageous. Symmetric nacnacRH are thus obtained in higher than 95% purity and with 65% yield for R = Me and 80%–95% yields for R = n-Pr, i-Pr, i-Bu, Bn, Cy, and (+)-CH(Me)Ph.

Reaction of N,N-dialkyl-2-amino-4-iminopent-2-enes (nacnac R H; R = Bn (1a), Cy (1b), R-CH-(Me)Ph (1c)) with nBuLi afforded the lithium salts nacnac R Li(THF), 2a-c. Further reaction with ZrCl 4 or ZrCl 4 (THF) 2 yielded the cis-dichloride complexes nacnac R 2 ZrCl 2 , 3a-c. As a side reaction in the synthesis of 3c, CH activation of CH(Me)Ph under formal HCl elimination was observed. Complex 3a could also be obtained by reaction of nacnac Bn H with nBu 2 ZrCl 2 . nacnac Bn 2 ZrMe 2 , 5, was formed in reactions of 3a with MeLi in the presence of excess AlMe 3 and was isolated from the reaction of Me 2 ZrCl 2 with 2a. Complex 5 reacts with aluminum chloride compounds, but not with lithium chloride, to form the dichloride complex 3a and with ethanol to form nacnac Bn 2 Zr(OEt) 2 , 6. X-ray diffraction studies have been performed for 3a-c, 5, and 6.

A cyclohexanediyl-bridged, bis(N-xylyl) diketiminate ligand, (±)-C6H10(nacnac(Xyl)H)2, LH2 (Xyl = 2,6-dimethylphenyl), was obtained from the reaction of [(2,6-dimethylphenyl)amino]-pent-3-en-2-one first with Meerwein's salt, then with (±)-cyclohexanediamine. The reaction of the ligand with Zr(NMe2)4 yielded LZr(NMe2)2. Protonation of the remaining diamide ligands with EtOH or [H2NMe2]Cl yielded LZr(OEt)2 and LZrCl2, respectively. The latter complex was also obtained by the reaction of LH2 first with nBuLi and then with ZrCl4(THF)2. The dichloride complex yielded LZr(OEt)2 and LZrMe2 upon reaction with NaOEt or MeLi/AlMe3, respectively. X-ray diffraction studies showed a trans-configuration of the ancillary ligands in LZrCl2 and LZrMe2, and a cis-configuration in LZr(NMe2)2 and LZr(OEt)2. LZr(OEt)2 was tested as a catalyst for the polymerization of rac-lactide. Kinetic investigations yielded a rate law first order in catalyst and monomer and a rate constant k = 14(1) L mol(-1) s(-1), the latter being orders of magnitude higher than typical activities for group 4 complexes in lactide polymerization. Analyses of the obtained polymer revealed an atactic polymer and broad polymer molecular weight distributions with sizeable fractions of cyclic oligomers. The influence of contaminants on the polymerization activity was examined: while lactic acid deactivates the catalyst, addition of up to 1 equiv. of water or para-toluenesulfonic acid revitalized catalysts not showing maximum activity.

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This paper reports the efficient synthesis of the first class of polyisobutylene(PIB)-supported palladium-PEPPSI precatalyst (PEPPSI = pyridine-enhanced precatalyst preparation, stabilization, and initiation). The new complexes are employed in Buchwald-Hartwig amination of aryl chlorides and are found to be reasonably active in the titled cross-coupling reaction. The supported catalysts are tested in polar (1,4-dioxane and 1,2-dimethoxyethane) as well as in aliphatic reaction media (toluene and n-heptane) and display superior activity in the highly lipophilic solvent (n-heptane). The catalytic efficacy of PIB-Pd-PEPPSI precatalyst is measured to be comparable to its nonsupported analog. Pd-leaching is determined by inductively coupled plasma mass spectrometry (ICP-MS) after a simple liquid/liquid extraction and is found to be 2 ppb in the product phase, translating into a recovery of ≈99.8% of the palladium.