Mechanism of the allylic rearrangement of allyloxo metal oxo complexes: An ab initio theoretical investigation

Chemistry - A European Journal

Volumn 5, Issue 1, 1999, Pages 57-64

  Bellemin Laponnaz, Stéphane ^a   Ny, Jean Pierre Le ^a   Dedieu, Alain ^a  

^a UNIVERSITÉ DE STRASBOURG   (France)

Author keywords

Ab initio calculations; Allyl alcohols; Homogeneous catalysis; Rhenium; Solvent effects

Indexed keywords

ALLYL ALCOHOL; ANION; CATION; HEX 1 EN 3 OL; HYDROXYL GROUP; METAL COMPLEX; ORGANOMETALLIC COMPOUND; TRIOXORHENIUM; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CATALYST; CIS TRANS ISOMERISM; ENERGY; OXIDATION; QUANTUM CHEMISTRY; SOLVATION;

EID: 0344076002     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19990104)5:1<57::AID-CHEM57>3.0.CO;2-B     Document Type: Article

References (62)

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17. Zero-point energies are not taken into account. The corresponding total energies (in Hartrees) are: 1: HF//HF -304. 7233; MP2//HF -304.5496; MP2//MP2 -304.5551; TS1: HF//HF -304. 6348; MP2// HF -305.4741; MP2//MP2 -305.4815; 2: HF//HF -494.3135; MP2// HF -495.8029; B3LYP//B3LYP -497.4682; TS2: HF//HF -494.2628; MP2//HF -495.7652; B3LYP//B3LYP -497.4371; 3a: HF//HF -343.7668; MP2//HF -344.7227; MP2//MP2 -344.7285; TS3b: HF// HF -343.6850; MP2//HF -344.6453; MP2//MP2 -344.6576; 3b: HF// HF -343.7672; MP2//HF -344.7208; MP2//MP2 -344.7266; 3a′: HF// HF -343.7603; MP2//HF -344.7169; MP2//MP2 -344.7227; TS3c: HF//HF -343.6801; MP2//HF -344.6453; MP2//MP2 -344.6541; 3c: HF//HF -343.7648; MP2//HF -344.7189; MP2//MP2 -344.7249; 4a: HF//HF -533.3590; MP2//HF -534.9787; TS4b: HF//HF -533.3152; MP2//HF -534.9394; 4b: HF//HF -533.3583; MP2//HF -534.9754; 4a′: HF//HF -533.3560; MP2//HF -534.9772; TS4c: HF//HF -533.3103; MP2//HF -534.9370; 4c: HF//HF -533.3550; MP2//HF -534.9726; 5: HF//HF -474.5969; MP2//HF -475.9092; TS5: HF// HF -474.5234; MP2//HF -475.8630.
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41. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
42. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
43. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
44. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
45. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
46. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
47. For theoretical studies of solvation effects on the Claisen rearrangement see ref. [14c] and: a) D. L. Severance, W. L. Jorgensen, J. Am. Chem. Soc. 1992, 114, 10966; b) C. J. Cramer, D. G. Truhlar, J. Am. Chem. Soc. 1992, 114, 8794; c) J. W. Storer, D. J. Giesen, G. D. Hawkins, G. C. Lynch, C. J. Cramer, D. G. Truhlar, D. A. Liotard, ACS Symp. Ser. 1994, 568, 24; d) J. Gao, J. Am. Chem. Soc. 1994, 116, 1563; e) A. Sehgal, L. Shao, J. Gao, J. Am. Chem. Soc. 1995, 117, 11337; f) R. J. Hall, M. M. Davidson, N. A. Burton, I. H. Hillier, J. Phys. Chem., 1995, 99, 921; g) M. M. Davidson, J. Phys. Chem. 1995, 99, 6748; h) J. M. Guest, J. S. Craw, M. A. Vincent, I. H. Hillier, J. Chem. Soc. Perkin Trans 2, 1997, 71;
48. J. J. Gajewski, Acc. Chem. Res. 1997, 30, 219.
49. [26]
50. W. A. Herrmann, W. Scherer, R. W. Fischer, J. Blümel, M. Kleine, W. Mertin, R. Gruehn, J. Mink, H. Boysen, C. C. Wilson, R. M. Ibberson, L. Bachmann, M. Mattner, J. Am. Chem. Soc. 1995, 117, 3231.
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52. 2O) on the other.
53. a) Y. Marcus, Ion Solvation, Wiley, Chichester, 1985.
54. See also b) G. Boche, Angew. Chem. 1992, 104, 742; Angew. Chem. Int. Ed. Engl. 1992, 31, 131.
55. See also b) G. Boche, Angew. Chem. 1992, 104, 742; Angew. Chem. Int. Ed. Engl. 1992, 31, 131.
56. 2O).
57. eq, respectively.
58. -1, which is also in good agreement with the HF//HF value.
59. eq.
60. The decrease in the negative charge of the metallic unit leads to a lowering of the orbitals of this unit, while the decrease of the positive charge of the allylic unit leads to a rise of the π orbitals of this unit. As a result, the energy gap between the two sets of orbitals becomes larger and the corresponding four-electron repulsions smaller.
61. -1 than the barrier for the [3,3] rearrangement.
62. -1 is close to the MP2//MP2 and B3LYP//B3LYP value.