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Treatment of N-aryl-2-methylquinolin-8-amines (L1-L3) with one equivalent AlMe3 or AlEt3 afforded dialkyl aluminum compounds (C1-C5), whereas the stoichiometric reaction of 2-((2-(1H-benzo[d]imidazol-2-yl)quinolin-8-ylimino)methyl)phenols (L4-L6) with either AlMe3 or AlEt3 produced monoalkyl aluminum compounds (C6-C10). All the organoaluminum compounds were characterized by 1H, 13C NMR and elemental analysis, and the molecular structures of representative compounds were confirmed by X-ray crystallography. With bidentate ligands, compounds C1 and C3 showed tetrahedron geometry around Al center, while compound C7 has a distorted square pyramidal geometry around Al center with the framework comprising the tetradentate ligand. The dialkyl aluminum compounds (C1-C5) performed high catalytic activities towards the ring opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL), in parallel, the monoalkyl aluminum compounds (C6-C10) showed negative results for the polymerization of epsilon-CL. In the presence or absence of benzyl alcohol (BnOH), the four-coordination aluminum compounds (C1-C5) are both highly active towards the ring opening polymerization (ROP) of epsilon-caprolactone with resulting high conversation of epsilon-caprolactone and polymers with high molecular weight. In the presence of one equivalent of BnOH, polymerization of epsilon-caprolactone proceeded in a living manner and molecular weights of the obtained poly(epsilon-caprolactone)s could be precisely controlled by adapting the reaction conditions.

A series of titanatranes containing both chelate bis(aryloxo)-(alkoxo)amine and the terminal aryloxo ligands of type [Ti(OAr)(L)](n) [n = 1 or 2, Ar = 2,6-Me(2)C(6)H(3) (1), 2,6-(i)Pr(2)C(6)H(3) (2), 2,6-Ph(2)C(6)H(3) (3), 2-FC(6)H(4) (4), 2,6-F(2)C(6)H(3) (5), C(6)F(5) (6); L = (O-2,4-Me(2)C(6)H(2)-6-CH(2))(2)(OCH(2)CH(2))N)] have been prepared, and their structures (1, 3-6) were determined by X-ray crystallography. The ortho-substituents in the terminal aryloxo ligand directly affect the structure in the solid state; the structures of 1-3 possessed monomeric form and fold a distorted trigonal bipyramidal geometry around Ti, whereas the structure of 4-6 were of dimeric form and fold a distorted octahedral around Ti bridged with oxygen in the alkoxo arm expressed as [Ti(OAr){(O-2,4-Me(2)C(6)H(2)-6-CH(2))(2)(mu(2)-OCH(2)CH(2))N)}](2). The Ti-O(Ar) bond distances and the Ti-O-C(Ar) bond angles are highly influenced by the terminal aryloxo substituents especially in the ortho-position. The 2,6-(i)Pr(2)C(6)H(3) analogue (2), the C(6)F(5) analogue (6), and the 2,6-Me(2)C(6)H(3) analogue (1) showed moderate/notable catalytic activities for ethylene polymerization in the presence of MAO especially at 80-100 degrees C, whereas both the 2,6-Ph(2)C(6)H(3) analogue (3) and 2-FC(6)H(4) analogue (4) showed the negligible catalytic activities, clearly indicating that the activity was strongly affected by the terminal aryloxo substituents especially in the ortho-position.

Cp*TiCl(2)(L) [L = C(3)H(3)N(2) (1), 3,5-Me(2)C(3)HN(2) (2) and 3,5-(i)Pr(2)C(3)HN(2) (3)], and Cp*Ti(C(3)H(3)N(2))(3) (4) were prepared in moderate yields by treating Cp*TiCl(3) with the pyrazoles in the presence of Et(3)N or with their corresponding lithium salts in Et(2)O. The structures of 1 and 2 determined by X-ray crystallography indicate that these complexes fold a distorted tetrahedral geometry around Ti, and the pyrazolato ligands coordinate to Ti with eta(2)-N,N'-coordination mode. In contrast, one of the pyrazolato ligand in 4 coordinates to Ti with eta(1)-N-bonding, whereas the other two ligands were bound to Ti with eta(2)-N,N'-fashion. The Cp analogues, CpTiCl(2)(L) [L = C(3)H(3)N(2) (5), 3,5-Me(2)C(3)HN(2) (6), 3,5-(i)Pr(2)C(3)HN(2) (7), and 3,5-Ph(2)C(3)HN(2) (8)], were also prepared by the reaction of CpTiCl(3) with the corresponding lithium salts in Et(2)O or n-hexane. The crystallographic analyses of 5 and 6 revealed that the pyrazolato ligands coordinate to Ti with eta(2)-N,N'-coordination mode. These complexes (1-3, 5-8) exhibited moderate catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO), and the activities were highly affected by the substituent on the pyrazolato ligand employed. Complex 1 exhibited the highest activity affording polymer with uniform molecular weight distribution, suggesting that the polymerization proceeded with uniform catalytically active species. An increase in the steric bulk in the pyrazolato ligand led to a slight decrease in the activity by the Cp* analogues, whereas the activity by the Cp analogues increased upon increasing the steric bulk in the pyrazolato ligand employed.

Al complexes containing phenoxy-imine ligands of type, Me2Al[O-2-R1-6-(R2N=CH)C6H3] [R1 = Me, R2 = 2,6-iPr2C6H3 (1a), tBu (1b); R1 = tBu, R2 = 2,6-iPr2C6H3 (2a), tBu (2b), cyclohexyl (2c), adamantyl (2d), C6H5 (2e), 2,6-Me2C6H3 (2f), C6F5 (2g)] have been prepared in high yields from AlMe3 by treating with 1.0 equiv. of 2-R1-6-(R2N=CH)C6H3OH in n-hexane. Structures for 1a, 1b, 2a-e and 2g were determined by X-ray crystallography, and these complexes have a distorted tetrahedral geometry around Al; both the Al-O and the Al-N bond distances were influenced by substituents in both the aryloxo and the imino groups. Me2Al[mu2-O-2-(R2N=CH)C6H4](AlMe3) [R2 = 2,6-iPr2C6H3 (3a), tBu (3b)] were prepared exclusively by reaction of AlMe3 with 2-(R2N=CH)C6H4OH, and these complexes form a distorted tetrahedral geometry around each Al centre with additional AlMe3 coordinating to the oxygen in the phenoxy-imine ligand. Complexes 1a, 1b and 2a-g were tested as catalyst precursors for ring-opening polymerisation (ROP) of epsilon-caprolactone (CL) in the presence of (n)BuOH (1.0 equiv. to Al), and their catalytic activities were strongly influenced by the imino substituent (R2). The efficient ROP has been achieved using the C6F5 analogue (2g), with the ROP taking place in a living manner.

A series of (1-adamantylimido)vanadium(V) complexes containing anionic donor ligands of the type, V(NAd)Cl2(L) [Ad = 1-adamantyl; L = O-2,6-Me2C6H3 (2), O-2,6-(i)Pr2C6H3 (3), NC(t)Bu2 (5), NC((t)Bu)CH2SiMe3 (6), NC((t)Bu)Ph (7), NCPh2 (8)], have been prepared from V(NAd)Cl 3, which was in turn prepared from VOCl3 by treatment with 1-adamantylisocyanate in octane, by treatment with the corresponding lithium salts (lithium phenoxides, lithium ketimides) in Et2O. These complexes (2, 3, 5-8) were identified by NMR spectroscopy and elemental analysis, and the structures for 2 and 5 were determined by X-ray crystallography. The reaction of V(NAd)Cl3 with 2,6-dimethylphenol in n-hexane afforded the tris(aryloxo) analogue V(NAd)(O-2,6-Me2C6H3)3 (4), the structure of which was determined by X-ray crystallography. 8 gradually decomposed in toluene to give a dimeric species, [N(Ad)H3](+)[V2(mu2-Cl)3Cl2(NAd)2(NCPh2)2](-) (10), but 8 was stabilized as a PMe 3 coordinated species, V(NAd)Cl2(NCPh2)(PMe3)2 (9): the structures for 9 and 10 were determined by X-ray crystallography. These complexes were evaluated as catalyst precursors for ethylene polymerization in the presence of MAO. The ketimide analogues, especially 5, exhibited moderate catalytic activity, and the activity with a series of V(NAd)Cl2(L)-MAO catalyst systems increased in the order: L = NC(t)Bu2 (5, 516 kg-PE/mol x V x h) > NC((t)Bu)Ph (7, 300) > NCPh2 (8, 105) > NC((t)Bu)CH2SiMe3 (6, 70.8). These complexes (2, 3, 5, 6) were found to be effective as catalyst precursors for the ring-opening metathesis polymerization (ROMP) of norbornene (NBE) in the presence of MeMgBr and PMe3.

Exclusive formation of poly(ethylene-co-styrene)s were observed by introduction of ethylene into the solution of syndiospecific styrene polymerisation using Cp'TiCl(2)(O-2,6-(i)Pr(2)C(6)H(3)) (Cp' = 1,2,4-Me(3)C(5)H(2), tert-BuC(5)H(4))-MAO catalysts without by-production of syndiotactic polystyrene, whereas the styrene polymerisation did not proceed when ethylene was removed from the reaction mixture of ethylene/styrene copolymerisation.

Various poly(macromonomer)s (PMMs) have been prepared by a repeating ring opening metathesis polymerization (ROMP) technique using the well-defined molybdenum initiators of the type, [Mo(CHCMe(2)Ph)(NAr)(OR)(2)] with OR=OCMe(3), OCMeC(CF(3))(2); Ar=2,6-iPr(2)C(6)H(3), 2,6-Me(2)C(6)H(3). The synthetic strategy is based on the polymerization of norbornene and its derivatives affording di- and triblock side chains bearing sugars (mannose, galactose, glucose etc.), linked via O- (ester), and glycosidase resistant C- (isoxazoline) glycosides. The efficient placement of norbornene units on the side chain termini and their conversion into PMMs, facilitated by the Mo alkylidenes, proceeded in a living manner with the quantitative initiation. The methodology was applied to prepare poly(macromonomer)-graft-PEG [PEG: poly(ethylene glycol)], by the attachment of a pseudo phenol terminus on the PMM main chain to PEG-Ms(2) [MsO(CH(2)CH(2)O)(n)Ms, Ms=MeSO(2)] using a "grafting to" approach. Removal of the acetal protecting groups from the sugar coating of a variety of supramolecular structures including PMMs, linear amphiphilic block copolymers (ABC) and a PMM-graft-PEGby using trifluroacetic acid/water (9:1), and suspension in water, prompted the spontaneous formation of spherical architectures by self-assembly of the amphiphilic PMMs as observed by transmission electron microscopy (TEM). The ability to uptake the hydrophobic dye (Nile Red) into the micellar cores of a variety of amphiphilic polymeric fragments is a significant step towards the production of sugar-coated nanospheres for cell-targeting biomimetic applications.

CpTiCl2(N=CtBu2) exhibits both remarkable catalytic activity and efficient norbornene (NBE) incorporation for ethylene-NBE copolymerization: the NBE incorporation by Cp'TiCl2(X) (X = N=CtBu2, O-2,6-iPr2C6H3; Cp' = Cp, C5Me5, indenyl) was related to the calculated coordination energy after ethylene insertion.

Various poly(macromonomer)s containing sugars have been prepared by ROMP of norbornene macromonomers substituted with ROMP block copolymers containing acetal-protected sugars as the side chain, which upon removal of the protecting group affords a novel amphiphilic architecture.