σ-Bond Metathesis Reactions Involving Palladium(II) Hydride and Methyl Complexes: A Theoretical Assessment

Inorganic Chemistry

Volumn 36, Issue 15, 1997, Pages 3223-3231

  Milet, Anne ^a   Dedieu, Alain ^a   Kapteijn, Gerard ^b   Van Koten, G ^b  

^a UNIVERSITÉ DE STRASBOURG   (France)

^b UTRECHT UNIVERSITY   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000735150     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic960807l     Document Type: Article

References (77)

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34. (c) Total MP2//MP2 energies (au): 1. -259.6011; TS1, -259.5810; 9, -259.6044; 2, -718.0434; TS2, -717.9773; 10, -717.9918; 3, -259.6509; TS3, -259.5913; 11, -259.6048; 4, -718.0329; TS4, -717.9819; 12, -717.9953; 5. -260.6733; TS5, -260.6482; 13, -260.6822; 6, -719.0944; TS6, -719.0217; 13, -719.0354; 7. -376.8608; TS7, -376.8418; 14, -376.8944; 8, -376.8901: TS8, -376.8509; 15, -376.8799.
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40. -1.
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49. 23
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52. 3 hydrogen atoms which was kept frozen during the optimization process. The corresponding eigenvectors are all similar to the one shown for TS1 in Chart 1. We have not carried out a frequency calculation for the much larger TS7 and TS7 structures, but the approximate Hessian obtained at the end of the geometry optimization was very similar to the ones obtained at the end of the geometry optimization of TS1-TS6.
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55. The H - Pd - O - H dihedral angles are 104.7, 121.8, 99.6, 93.1, 101.0. and 109.1° in TS1-TS6, respectively.
56. 29
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60. These values were computed at the MP2 level on the optimized structures of 1 and 2 modified by elongating the Pd - H bond up to 1.89 and 1.68 Å, respectively (these values are the ones found for TS1 and TS2).
61. We note that, in 5, the hydride is only slightly negative. But in 6, H is positively charged. Thus, the correlation still holds for this set of two reactions.
62. The contour diagrams have been obtained by using the MOLDEN package. MOLDEN was written by G. Schaftenaar, CAOS/CAMM Center Nijmegen, The Netherlands, 1991.
63. 35
64. Riehl, J. F.; Jean, Y.; Eisenstein, O.; Pélissier, M. Organometallics 1992, 11, 729.
65. 2O a lone pair with Pd. This compromise results in quite long Pd-H bonds and a larger Pd - O - H angle.
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69. 2O is a relay for the transfer of one hydrogen of the amine ligand to the hydride.
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72. 42 one may expect the associative pathway to be favored with an energy barrier of a few kilocalories per mole.
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74. This feature is quite general and has been found for other oxidative addition reactions involving Pd(II)/Pd(IV) oxidation states: Milet, A.; Dedieu, A. Unpublished results.
75. 3 density and then augmenting the radius corresponding to this volume by 0.5 Å).
76. -1.
77. Musaev, D. G.; Svensson, M.; Morokuma, K.; Strömberg, S.; Zetterberg, K.; Siegbahn, P. E. M. Organometallics 1997, 16, 1933.