Theoretical Study of Oxidative Addition and Reductive Elimination of 14-Electron d10 ML2 Complexes: A ML2 + CH4 (M = Pd, Pt; L = CO, PH3, L2 = PH'2CH2CH2PH2) Case Study

Inorganic Chemistry

Volumn 37, Issue 13, 1998, Pages 3400-3406

  Su, Ming Der ^a   Chu, San Van ^a  

^a NATIONAL TSING HUA UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000856006     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic970320s     Document Type: Article

References (66)

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2. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
3. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
4. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
5. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
6. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
7. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
8. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
9. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
10. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113. (b) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New York, 1989. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41. (d) Ephritikhinc, M. New J. Chem. 1986, 10, 9. (e) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (f) Ryabov, A. D. Chem. Rev. 1990, 90, 403. (g) Davies. J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers Inc.: New York. 1990. (h) Bergman. R. G. Adv. Chem. Ser. 1992, 230, 211. (i) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789. (j) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937. (k) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 26, 154. (l) Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
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49. 2 (+0.643). Thus, our computational evidence clearly shows that the electron-donating ability decreases in the same order as we predicted in the article.
50. 2.
51. As shown in Table 1, in the case of the Pd series, it was found that the MP2 calculations yield the transition state being more stable than the product, implying that those product optimizations were artificial. Reducing optimization convergence criteria by an order of magnitude still did not change the situation. It appears that the potential energy surfaces for the Pd product complexes are fairly flat. A set of polarization functions on Pd and the ligands and the inclusion of correlation should be essential. This study is, however, beyond the scope of the present work. Nevertheless, our study shows that the single-point MP4 calculations based on the MP2 geometries can provide reliably qualitative conclusions.
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63. At the MP2/LANL2DZ level, the linear relationship is y = 0.766x -21.0.
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66. 2) involved in Figure 2, in the CpCoL case there could be three predominant configurations contributing to the total wave function ψ, i.e., a closed-shell singlet, two open-shell triplets (so overall singlet), and un open-shell singlet. This study, however, is beyond the scope of the present work and will not be discussed here.