Syntheses, Structures, Reactivities, and Basicities of Quinolinyl and Isoquinolinyl Complexes of an Electron Rich Chiral Rhenium Fragment and Their Electrophilic Addition Products.

Reactions of Li+ [(η5 -C5 H5 )Re(NO)(PPh3 )]- with 2- and 4-chloroquinoline or 1-chloroisoquinoline give the corresponding σ quinolinyl and isoquinolinyl complexes 3, 6, and 8. With 3 and 8 there is further protonation to yield HCl adducts, but additions of KH give the free bases. Treatment of 3 with HBF4 ⋅OEt2 or H(OEt2 )2 + BArf - gives the quinolinium salts [(η5 -C5 H5 )Re(NO)(PPh3 )(C(NH)C(CH)4 C(CH)(CH))]+ X- (3-H+ X- ; X- =BF4 - /BArf - , 94-98 %). Addition of CF3 SO3 CH3 to 3, 6, or 8 affords the corresponding N-methyl quinolinium salts. In the case of [(η5 -C5 H5 )Re(NO)(PPh3 )(C(NCH3 )C(CH)4 C(CH)(CH))]+ CF3 SO3 - (3-CH3 + CF3 SO3 - ), addition of CH3 Li gives the dihydroquinolinium complex (SRe RC ,RRe SC )-[(η5 -C5 H5 )Re(NO)(PPh3 )(C(NCH3 )C(CH)4 C(CHCH3 )(CH2 ))]+ CF3 SO3 - ((SRe RC ,RRe SC )-5+ CF3 SO3 - , 76 %) in diastereomerically pure form. Crystal structures of 3-H+ BArf - , 3-CH3 + CF3 SO3 - , (SRe RC , RRe SC )-5+ Cl- , and 6-CH3 + CF3 SO3 - show that the quinolinium ligands adopt Re⋅⋅⋅C conformations that maximize overlap of their acceptor orbitals with the rhenium fragment HOMO, minimize steric interactions with the bulky PPh3 ligand, and promote various π interactions. NMR experiments establish the Brønsted basicity order 3>8>6, with Ka (BH+ ) values >10 orders of magnitude greater than the parent heterocycles, although they remain less active nucleophilic catalysts in the reactions tested. DFT calculations provide additional insights regarding Re⋅⋅⋅C bonding and conformations, basicities, and the stereochemistry of CH3 Li addition.

[n]-Oligourea-Based Green Sorbents with Enhanced CO2 Sorption Capacity.

A new series of [n]-oligoureas ([n]-OUs, n=4, 7, 10, and 12) green solid sorbents was prepared following a base-catalyzed, microwave-assisted oligomerization reaction. The materials were characterized by NMR and IR spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and XRD. Decomposition temperatures at 50 % weight loss (Td50 ) were ca. 350 °C for all oligomers. Urea and urethane functional groups indicated by IR spectroscopy confirmed the formation of the sorbent. The CO2 capturing capacities were determined at 35 °C and 1.0 bar (gravimetric method). Accordingly, [10]-OU had the highest CO2 sorption capacity among the others (18.90 and 22.70 mg CO 2 gsorbent (-1) ) at two different activation temperatures (60 or 100 °C, respectively). Chemisorption was the principal mechanism for CO2 capture. Cyclic CO2 sorption/desorption measurements were carried out to test the recyclability of [10]-OU. Activating the sample at 60 °C, three stable CO2 sorption cycles were achieved after running the first cycle.