A new synthetic methodology for adding carbon-based nucleophiles to the carbocyclic ring of quinolines has been developed, based on the electron-deficient bonding of the C(8) carbon and the protective coordination of the nitrogen atom to the metal core in the complexes Os 3 (CO) 9 (µ 3 -η 2 -C 9 H 5 (R)N)(µ-H), 1a-1h. These compounds react with a wide range of carbanions (e.g., R′Li) to give the nucleophilic addition products Os 3 (CO) 9 (µ 3 -η 3 -C 9 H 7 (5-R′)N)(µ-H), 2a-2l, and Os 3 (CO) 9 (µ 3 -η 3 -C 9 H 6 (3-, 4-, or 6-R)(5-R′)N)(µ-H), 3b-3g, after quenching with trifluoroacetic acid, in isolated yields of 25-86%. In the 6-substituted derivatives, this addition is stereoselective, forming only the cis-diastereomer. In the case the 6-chloro derivative, a second product is obtained, Os 3 (CO) 9 (µ 3 -η 2 -C 9 H 5 (6-Cl)(5-C(CH 3 ) 2 CN)N)(µ-H) 2 , 4, the result of protonation at the metal core and rearrangement of the carbocyclic ring. The trans-diastereomer of the 6-substituted derivatives can be obtained by quenching the intermediate anion of the unsubstituted complex with (CH 3 O) 2 SO 2 or acetic anhydride. Nucleophilic addition to the 5-chloro complex occurs across the 3,4-bond to give Os 3 (CO) 9 (µ 3η 2 -C 9 H 6 (5-Cl)(4-C(CH 3 ) 2 CN)N)(µ-H), 5. The addition products, types 2 and 3, can be rearomatized by reaction with diazobicyclononane (DBU)/dichlorodicyanoquinone (DDQ) or by reaction of the intermediate anion with trityl cation or DDQ. The resulting rearomatized complexes can be cleanly cleaved from the cluster by heating in acetonitrile under a CO atmosphere, yielding the functionalized quinoline and Os 3 (CO) 12 as the only two products. Solid structures of cis-3e, trans-3e, 4, and 5 are reported.

Electrochemically grown films of polyaniline, polypyrrole, polythiophene, and poly(ethylenedioxythiophene) were treated with alkane-and fluoroalkanethiols for 1-24 h. The resulting films showed surface energies and polarities similar to glass slides coated with monolayers of the corresponding alkyl-and fluoroalkylsilanes. Treatment of the polyaniline, polypyrrole, and, to a lesser extent, poly-(ethylenedioxythiophene) films resulted in covalent bonding of the thiol to the polymer backbone as evidenced by X-ray photoelectron, energy-dispersive X-ray, and electronic spectroscopies. Polypyrrole and poly(ethylenedioxythiophene) films showed reduced electroactivity upon treatment, while the derivatized polyaniline could be returned to a conducting state. Polythiophene primarily oxidized the thiols to soluble products, leaving the polymer backbone unaffected.

The reactions of the cluster complexes Os 3 -(CO) 9 (µ 3 -η 3 4), and Os 3 (CO) 9 (µ 3 - 5) with para-hydrogen have been studied at ∼3 atm and 90-110 °C. In all cases, reaction at the metal core is the initial product and polarization enhanced polyhydride intermediates are observed. The chemical shifts and relative intensities of these resonances are used to extract mechanistic information about the reactivity of 1-5. As with previous studies on related electron-deficient complexes, 3-5 show reactivity that is very sensitive to the substituent in the 5-position.

No abstract

No abstract

No abstract

No abstract

No abstract