New easily accessible 1,1'-bi-2-naphthol- (BINOL-) and biphenanthrol-based chiral pincer complex catalysts were prepared for selective (up to 85% enantiomeric excess) allylation of sulfonimines. The chiral pincer complexes were prepared by a flexible modular approach allowing an efficient tuning of the selectivity of the catalysts. By employment of the different enantiomeric forms of the catalysts, both enantiomers of the homoallylic amines could be selectively obtained. Both allyl stannanes and allyl trifluoroborates can be employed as allyl sources in the reactions. The biphenanthrol-based complexes gave higher selectivity than the substituted BINOL-based analogues, probably because of the well-shaped chiral pocket generated by employment of the biphenanthrol complexes. The enantioselective allylation of sulfonimines presented in this study has important implications for the mechanism given for the pincer complex-catalyzed allylation reactions, confirming that this process takes place without involvement of palladium(0) species.

Palladium-catalyzed condensation reactions of sulfonimines with isocyanoacetate were performed using various PCP, SCS, SeCSe and NCN pincer complexes as catalysts. The reactions proceeded rapidly (2 h) at room temperature using only 1 mol % pincer complex catalyst without any additives. The electron-deficient and relatively bulky PCP complex provides imidazoline derivatives with a very high syn diastereoselectivity. The applied PCP catalyst proved to be very robust under the applied reaction conditions, as it could be recovered without any decomposition after the completed catalytic process. The stereoselectivity of the condensation reactions is reversed by employing the electron-rich SeCSe type of complexes. Simple palladium salts, such as palladium acetate, PdA C H T U N G T R E N N U N G (OAc) 2 , catalyze the reaction with a poor stereoselectivity. The stereoselectivity of the PCP complex-catalyzed process does not depend significantly on the steric bulk of the sulfonimine component. Mechanistic studies revealed that the PCP complex-catalyzed reaction proceeds via an h 1 -coordinated palladium isocyanoacetate pincer intermediate. This intermediate could also be isolated and its structure was determined by X-ray diffraction. The X-ray structure of this reaction intermediate indicates a surprisingly strong carbon-metal bond between the palladium atom and the coordinated isocyanoacetate molecule. Our mechanistic studies show that the pincer complex catalyst does not undergo redox reactions and, thus it retains a + 2 oxidation state under the catalytic process.

The tunable self-assembly of a fullerene (C(60))-N,N-dimethylaminoazobenzene (DPNME) molecular system as a function of solvent polarity in THF/water binary solvent is reported. Gradual increase of the volume fraction of the nonsolvent water in a 1×10(-5) M THF solution of DPNME at a mixed dielectric constant ε(mix)≈42 resulted in initial redshifting of the (1)(π→π(*)) absorption band, which signified the 1D head-to-tail or J-type arrangement of the DPNME molecular system. Further increase in the solvent polarity to ε(mix)≈66 evidenced formation of an antiparallel head-to-tail or H-type molecular arrangement in conjunction with the J-aggregates, thereby establishing a solvent-polarity-dependent dynamic equilibrium between the monomer ↔ J-aggregate ↔ H-aggregate. The controlled aggregation was governed by the synergetic effect of intermolecular donor-acceptor interaction between the electron-deficient fullerene ring and the electron-rich N,N-dimethylamino-substituted aromatic ring; typically, van der Waals and π-π interactions between the molecules constituting a pair of dimers were envisaged. An agreement between the semiempirically calculated drastically reduced oscillator strength of the DPNME H-dimer in the antiparallel configuration (0.69 vs. 1.29 in the monomeric DPNME) and the experimental electronic absorption spectra beyond ε(mix)=66 further strengthened this assignment to the hitherto forbidden antiparallel H-dimer. Complementing the above, the periodicity of molecular self-assembly dictated a monoclinic unit cell in the single-crystal XRD packing pattern with a C2/c space group; the molecules packed laterally with mutual interdigitation with the donor (E)-N,N-dimethyl-4-(p-tolyldiazenyl)aniline (AZNME) parts in an antiparallel fashion (contrary to the usual expectation for H-aggregates) with strong inter- and intrapair van der Waals and π-π interactions between the constituent fullerene moieties. Unlike those of porphyrin/phthalocyanine bowl-like donor-initiated architectures, a rare class of DPNME dyadic supramolecular self-assemblies was realized with π-extended 2D fullerene networks, in which the linear geometry of the AZNME donor and the conformational rigidity of the fullerene acceptor played crucial roles.

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The compounds [CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 ]PCl (1), (OCH 2 CMe 2 CH 2 O)-PCl (2), and [ClPN(t-Bu)] 2 (3) have been utilized as precursors in the synthesis of (i) new pentacoordinate phosphorus compounds [e.g. CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 P(NRR′)(O 2 C 6 Cl 4), CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 PX[OC(O-i-Pr)N=N(C(O)O-i-Pr)], (ii) cyclic phosphates and their complexes [e.g. {imidazolium} + {CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 PO 2 }-.MeOH], (iii) new cycloaddition products [e.g. {CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 }P{C(CO 2 Me)C(CO 2 Me)C(O)N}, (iv) macrocyclic compounds [e.g. {[(t-BuN)P] 2 [-OCH 2 CMe 2 CH 2 O-]} 2 ] and (v) phosphonates [e.g. (OCH 2 CMe 2 CH 2 O)P (O)CH 2 C(CN)=CHC 5 H 4 FeC 5 H 5 ]. The synthetic and structural aspects of these new products are discussed.

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