The metal is the kinetic site of protonation of (Diimine)Pt dimethyl complexes

Journal of the American Chemical Society

Volumn 124, Issue 41, 2002, Pages 12116-12117

  Wik, Bror Johan ^a   Lersch, Martin ^a   Tilset, Mats ^a  

^a UNIVERSITY OF OSLO   (Norway)

Author keywords

[No Author keywords available]

Indexed keywords

IMINE; METAL COMPLEX; METHYL GROUP; PLATINUM COMPLEX;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; PROTON TRANSPORT;

EID: 0037120895     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027649j     Document Type: Article

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39. 1H NMR.
40. 2 (200 - x μL.; x = 0-200 μL). The tube was capped, kept at -78 °C, and shaken to mix the reactants immediately before transfer to a precooled NMR probe. A pale, homogeneous yellow solution was immediately obtained. Particular care was taken to minimize any heating of the sample. The product distributions at -40 °C are not very different from those at -78 °C, suggesting that unintentional heating did not perturb the results.
41. The observed 5:4 product yields and ratios were unchanged after 2 h at -78 °C, indicating that 2 is irreversibly trapped by MeCN (otherwise, more 5 should be formed over time). Heating resulted in elimination of methane from 4, yielding more 5.
42. Pt-H = 1547 Hz). Additional NMR data for 4 are given in the Supporting Information.
43. Pt-H = 1547 Hz). Additional NMR data for 4 are given in the Supporting Information.
44. Pt-H = 1547 Hz). Additional NMR data for 4 are given in the Supporting Information.
45. 3 signals of 4 and 5. In cases where relative yields of 4 and 5 could be determined from nonoverlapping diimine ligand signals, the results were identical within experimental uncertainties.
46. 2 complex) precedes dihydride formation. Papish, E. T.; Rix, F. C.; Spetseris, N.; Norton, J. R.; Williams, R. D. J. Am. Chem. Soc. 2000, 122, 12235.
47. We cannot rule out that the steric effect is caused by protonation at methyl as a minor reaction pathway.