López-Serrano, J., Duckett, S.B., Aiken, S., Almeida Leñero, K.Q., Drent, E., Dunne, J.P., Konya, D. and Whitwood, A.C. (2007) A para-hydrogen investigation of palladium-catalyzed alkyne hydrogenation. Journal of the American Chemical Society, 129 (20). pp. 6513-6527. ISSN 0002-7863
The complexes [Pd(bcope)(OTf)2] (1a), where bcope is (C8H14)PCH2−CH2P(C8H14), and [Pd(tbucope)(OTf)2] (1b), where tbucope is (C8H14)PC6H4CH2P(tBu)2, catalyze the conversion of diphenylacetylene to cis- and trans-stilbene and 1,2-diphenylethane. When this reaction was studied with para-hydrogen, the characterization of [Pd(bcope)(CHPhCH2Ph)](OTf) (2a) and [Pd(tbucope)(CHPhCH2Ph)](OTf) (2b) was achieved. Magnetization transfer from the α-H of the CHPhCH2Ph ligands in these species proceeds into trans-stilbene. This process has a rate constant of 0.53 s-1 at 300 K in methanol-d4 for 2a, where ΔH = 42 ± 9 kJ mol-1 and ΔS = −107 ± 31 J mol-1 K-1, but in CD2Cl2 the corresponding rate constant is 0.18 s-1, with ΔH = 79 ± 7 kJ mol-1 and ΔS = 5 ± 24 J mol-1 K-1. The analogous process for 2b was too fast to monitor in methanol, but in CD2Cl2 the rate constant for trans-stilbene formation is 1.04 s-1 at 300 K, with ΔH = 94 ± 6 kJ mol-1 and ΔS = 69 ± 22 J mol-1 K-1. Magnetization transfer from one of the two inequivalent β-H sites of the CHPhCH2Ph moiety proceeds into trans-stilbene, while the other site shows transfer into H2 or, to a lesser extent, cis-stilbene in CD2Cl2, but in methanol it proceeds into the vinyl cations [Pd(bcope)(CPhCHPh)(MeOD)](OTf) (3a) and [Pd(tbucope)(CPhCHPh)(MeOD)](OTf) (3b). When the same magnetization transfer processes are monitored for 1a in methanol-d4 containing 5 μL of pyridine, transfer into trans-stilbene is observed for two sites of the alkyl, but the third proton now becomes a hydride ligand in [Pd(bcope)(H)(pyridine)](OTf) (5a) or a vinyl proton in [Pd(bcope)(CPhCHPh)(pyridine)](OTf) (4a). For 1b, under the same conditions, two isomers of [Pd(tbucope)(H)(pyridine)](OTf) (5b and 5b‘) and the neutral dihydride [Pd(tbucope)(H)2] (7) are detected. The single vinylic CH proton in 3 and the hydride ligands in 4 and 5 appear as strong emission signals in the corresponding 1H NMR spectra.
|Institution:||The University of York|
|Academic Units:||The University of York > Chemistry (York)|
|Depositing User:||York RAE Import|
|Date Deposited:||03 Apr 2009 10:45|
|Last Modified:||03 Apr 2009 10:45|
|Publisher:||ACS American Chemical Society|