The iminophosphinimide complexes [Ar(R)N]3M(NPNBut) (M = V, Nb) were prepared from the corresponding anionic nitride species ([Ar(R)N]3M identical to NNa)2 by way of a four-step synthetic strategy.

Organic-inorganic hybrid nano-building blocks of aromatic nitro-, aldehyde-, and bromo-functionalized polyhedral oligomeric silsesquioxanes were easily prepared through nucleophilic substitutions, starting from the reactions between octakis(3-chloropropyl)octasilsesquioxane and phenoxide derivatives. These phenoxide anions not only supply the substitution functions to a silsesquioxane cage, but can also induce a cage-rearrangement leading to the formation of octa-, deca-, and dodecahedral silsesquioxane cages.

Three aluminium alkoxide complexes containing N(2)O(2) bis(phenoxy)-amine ligands were synthesized from reactions of the corresponding N(2)O(2) ligands with Al(O(i)Pr)(3) in toluene. Different amine side chains of the ligands included pyridine (1), CH(2)NMe(2) (2), and CH(2)NEt(2) (3). The related chloro aluminium analog (4) was prepared from a reaction between AlCl(3) and the potassium salt of the N(2)O(2) ligand having CH(2)NMe(2) side chain. X-Ray crystallography reveals that complexes 3 and 4 have a monomeric five-coordinate aluminium center. Complexes 1-3 catalyzed the polymerization of epsilon-caprolactone (epsilon-CL) at 70 degrees C in toluene with the relative reactivities of 1<2< 3. In contrary, only complex 1 was active for the polymerization of lactide under the same polymerization conditions. (1)H NMR spectroscopy shows that treatment of 2 with 1 equivalent of lactide afforded the ring-opened product L(2)Al-OCH(Me)C(O)OCH(Me)C(O)O(i)Pr. Electronic effects are believed to be responsible for the observed trend in the epsilon-CL polymerization rates. On the other hand, steric hindrance at the amine side chain is the main contributor to the observed rates of lactide polymerization.

Polyhedral oligomeric silsesquioxane (POSS)-based materials, poly-POSS-T [n = 8 (1), 10 (2), 12 (3), and mix (4)], were prepared in high yields via free radical polymerization of corresponding pure forms of methacrylate-functionalized POSS monomers, MMA-POSS-T (n = 8, 10, 12), and the mixture form, MMA-POSS-T. Powder X-ray diffraction (XRD) spectra and BET analysis indicate that 1-4 are amorphous materials with high surface areas (683-839 m g). The surface areas and total pore volumes follow the trend: poly-POSS-T > poly-POSS-T > poly-POSS-T > poly-POSS-T. In addition, on the basis of Barrett-Joyner-Halenda (BJH) analysis, poly-POSS-T contains the highest amount of mesopores. The Pd nanoparticles immobilized on poly-POSS-T [n = 8 (5), 10 (6), 12 (7), and mix (8)] are well dispersed with 4-6 wt % Pd content and similar average particle sizes of 6.2-6.5 nm, according to transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) and microwave plasma-atomic emission spectroscopy (MP-AES). At 90 °C, the stabilized Pd nanoparticles in 5-8 catalyzed aerobic oxidation of benzyl alcohol to benzaldehyde in 72-100% yields at 6 h using a mixture of a HO/Pluronic (P123) solution. The PdNp@poly-POSS-T catalyst (5) exhibited the lowest catalytic activity, as a result of its lowest surface areas, total pore volumes, and amounts of mesopores. With the catalyst 8, various benzyl alcohol derivatives were converted to the corresponding aldehydes in good to excellent yields. However, with alcoholic substrates featuring electron-withdrawing substituents, high conversions were achieved with 1 equiv of KCO additive and longer reaction times.

A series of bis(amidinate) tin(II) complexes is synthesized and shown to rapidly polymerize ε-caprolactone (ε-CL) in the presence and absence of benzyl alcohol giving high-molecular-weight poly(ε-CL) (M(n) up to 160,600 Da). Ligands having electron donating groups were found to accelerate the polymerization by making the complex more nucleophilic.