A computational study of reductive elimination reactions to form C-H bonds from Pt(II) and Pt(IV) centers. Why does ligand loss precede reductive elimination from six-coordinate but not four-coordinate platinum?

Journal of the American Chemical Society

Volumn 122, Issue 7, 2000, Pages 1456-1465

  Bartlett, Kevin L ^a   Goldberg, Karen I ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; HYDROGEN; LIGAND; METHANE; PLATINUM;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; DISSOCIATION; ENERGY; ENTHALPY; GEOMETRY; HYDROGEN BOND; ISOMER; MATHEMATICAL ANALYSIS; REDUCTION;

EID: 0033995433     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9915706     Document Type: Article

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51. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
52. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
53. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
54. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
55. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
56. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
57. Examples of alkyl C-C reductive elimination from octahedral Pt(IV), Pd(IV): (a) Williams, B. S.; Holland, A. W.; Goldberg, K. I. J. Am. Chem. Soc. 1999, 121, 252. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) Hill, G. S.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1999, 18, 1408. (d) Roy, S.; Puddephatt, R. J.; Scott, J. D. J. Chem. Soc., Dalton Trans. 1989, 2121. (e) Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E. J. Chem. Soc., Dalton Trans. 1974, 2457. (f) Canty, A. J. Acc. Chem. Res. 1992, 25, 83 and references therein. (g) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J. D. Organometallics 1988, 7, 1363. (h) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989, 8, 2907. (i) van Asselt, R.; Rijnberg, E.; Elsevier: C. J. Organometallics 1994, 13, 706. (j) Crumpton, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2000, 122, 962.
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84. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.6; Gaussian, Inc.: Pittsburgh, PA, 1998.
85. Schmid, R.; Herrmann, W. A.; Frenking, G. Organometallics 1997, 16, 101.
86. Table S-1 of the Supporting Information gives uncorrected CCSD-(T) and B3LYP energies and the basis set superposition errors for each. Unlike B3LYP, CCSD(T) uses virtual orbitals for electron correlation, so basis set superposition causes larger errors in CCSD(T) calculations than in B3LYP calculations.
87. ‡ ≈ 0.
88. 3 ligands with added phosphine should be competitive with direct reductive elimination from 1.
89. 3 ligands also raises the barrier for direct elimination by ∼3 kcal/mol. Thus, these two effects of methyl substituents on the competition between ligand loss and direct elimination appear to cancel partially.
90. 6g,l
91. Åkermark, B.; Ljungqvist, A. J. Organomet. Chem. 1979, 182, 59.
92. 3)H.
93. When a partial optimization of 2 + 2Cl was conducted with only the H-Pt-C angle fixed, using the angle in transition structure 2, the phosphine ligand trans to the hydride moved away from the metal center to a distance greater than 4 Å. This finding is consistent with the result obtained when the direct elimination of methane from 13c was investigated.