Zwitterionic and cationic bis(phosphine) platinum(II) complexes: Structural, electronic, and mechanistic comparisons relevant to ligand exchange and benzene C-H activation processes

Journal of the American Chemical Society

Volumn 125, Issue 29, 2003, Pages 8870-8888

  Thomas, J Christopher ^a   Peters, Jonas C ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

LIGANDS; METALATION PROCESSES;

ACTIVATION ENERGY; COMPLEXATION; DIMERS; HYDROGEN BONDS; ION EXCHANGE; MOLECULAR STRUCTURE; THERMAL EFFECTS;

PLATINUM COMPOUNDS;

AMPHOLYTE; BENZENE; BIS(PHOSPHINE) PLATINUM; BORIC ACID; CARBON; CARBONYL DERIVATIVE; CATION; DIPHENYLBORATE; HYDROGEN; LIGAND; METHANE; MOLYBDENUM; PHENYL GROUP; PHOSPHINE; PLATINUM; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; ELECTRON; ELECTRONICS; LIGAND BINDING; MOLECULAR STABILITY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SPECTROSCOPY; TEMPERATURE DEPENDENCE;

EID: 0041313997     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0296071     Document Type: Article

References (89)

1. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
2. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
3. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
4. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
5. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
6. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
7. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
8. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
9. For a few examples of cationic metal-mediated bond-forming and polymerization reactions, see: (a) Schrock, R. R.: Osbom, J. A. J. Am. Chem. Soc. 1971, 93, 3089-3091. (b) Crabtree, R. H. Acc. Chem. Res. 1979, 12, 331-337. (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.; Imamoto, T. Org. Lett. 2001, 3, 1701-1704. (d) Oi, S.; Terada, E.; Ohuci, K.; Kato, T.; Tachibana, Y.; Inoue, Y. J. Org. Chem. 1999, 64. 8660-8667. (e) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999. 1, 2157-2159. (f) Madine, J. W.; Wang, X.; Widenhoefer, R. A. Org. Lett. 2001, 3, 385-388. (g) LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. (h) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (i) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
10. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
11. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
12. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
13. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
14. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
15. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
16. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
17. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
18. Recent summaries and examples of cationic metal-mediated C-H bond activation and functionalization include: (a) Amdtsen, B. A.; Bergman, R. G.: Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162. (b) Lohrenz, J. C. W.: Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996. 35, 1305-1307. (c) Sen, A. Acc. Chem. Res. 1998, 31. 550-557. (d) Stahl, S. S.: Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2181-2192. (e) Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 122, 9427-9434. (f) Tellers, D. M.; Bergman, R. G. J. Am. Chem. Soc. 2000, 122, 954-955. (g) Crabtrec, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437-2450. (h) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (i) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer: Boston, 2000.
19. (a) Thomas, J. C.; Peters, J. C. J. Am. Chem. Soc. 2001, 123, 5000-5001.
20. (b) Lu, C. C.: Peters, J. C. J. Am. Chem. Soc. 2002, 124, 5272-5273.
21. (c) Jenkins, D. M.; Betley, T. A.: Peters, J. C. J. Am. Chem. Soc. 2002, 124, 11238-11239.
22. (d) Jenkins, D. M.; Di Bilio, A. J.; Allen, M. J.; Betley. T. A.; Peters, J. C. J. Am. Chem. Soc. 2002, 124, 15 336-15 350.
23. (e) Brown, S. D.; Betley, T. A.; Peters, J. C. J. Am. Chem. Soc. 2003, 125, 322-323.
24. (f) Betley, T. A.; Peters, J. C. Inorg. Chem. 2002, 41, 6541-6543.
25. (g) Betley, T. A.; Peters, J. C. Angew. Chem., Int. Ed. 2003, 42, 2385-2389.
26. (a) Hoic, D. A.; Davis, W. M.; Fu, G. C. J. Am. Chem. Soc. 1996, 118, 8176-8177.
27. (b) Seymore, S. B.; Brown, S. N. Inorg. Chem. 2000, 39, 325-332.
28. (c) Padilla-Martínez, I. I.; Poveda, M. L.: Carmona, E.; Monge, M. A.; Ruiz-Valero, C. Organometallics 2002, 21, 93-104.
29. (a) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1995, 117, 9371-9372.
30. (b) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961-5976.
31. (a) Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119. 848-849.
32. (b) Holtcamp, M. W.; Henling, L. M.; Day, M. W.; Labinger, J. A.; Bercaw, J. E. Inorg. Chim. Acta 1998, 270, 467-478.
33. Zhong, H. A.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2002, 124, 1378-1399.
34. (a) Wick, D. D.; Goldberg, K. I. J. Am. Chem. Soc. 1997, 119, 10 235-10 236.
35. (b) Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Science 1998, 280, 560-564.
36. (c) Vedernikov, A. N.: Caulton, K. G. Angew. Chem., Int. Ed. 2002, 41. 4102-4104.
37. (a) Johansson, L.; Ryan, O. B.; Tilset, M. J. Am. Chem. Soc. 1999, 121, 1974-1975.
38. (b) Heiberg, H.; Johannson, L.; Gropen, O.; Ryan, O. B.; Swang, O.; Tilset, M. J. Am. Chem. Soc. 2000, 122, 10 831-10 845.
39. (c) Johansson, L.; Tilset, M.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2000. 122, 10 846-10 855.
40. (d) Johannson, L.; Tilset, M. J. Am. Chem. Soc. 2001, 123, 739-740.
41. (e) Johansson, L.; Ryan, O. B.; Rømming, C.; Tilset, M. J. Am. Chem. Soc. 2001, 123, 6579-6590.
42. (a) Reinartz, S.; White, P. S.: Brookhart, M.; Templeton, J. L. Organometallics 2001, 20, 1709-1712.
43. (b) Reinartz, S.; White, P. S.; Brookhart M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 123, 12 724-12 725.
44. Other phosphine-supported platinum(II) systems which have demonstrated C-H bond activation include: (a) Brainard, R. L.; Nutt, W. R.; Lee, T. R.; Whitesides, G. M. Organometallics 1988, 7, 2379-2386. (b) Peters, R. G.; White, S.; Roddick, D. M. Organometallics 1998, 17, 4493-4499. (c) Edelbach, B. L.; Lachichotte, R. J.; Jones, W. D. J. Am. Chem. Soc. 1998, 120, 2843-2853. See also ref 12.
45. Other phosphine-supported platinum(II) systems which have demonstrated C-H bond activation include: (a) Brainard, R. L.; Nutt, W. R.; Lee, T. R.; Whitesides, G. M. Organometallics 1988, 7, 2379-2386. (b) Peters, R. G.; White, S.; Roddick, D. M. Organometallics 1998, 17, 4493-4499. (c) Edelbach, B. L.; Lachichotte, R. J.; Jones, W. D. J. Am. Chem. Soc. 1998, 120, 2843-2853. See also ref 12.
46. Other phosphine-supported platinum(II) systems which have demonstrated C-H bond activation include: (a) Brainard, R. L.; Nutt, W. R.; Lee, T. R.; Whitesides, G. M. Organometallics 1988, 7, 2379-2386. (b) Peters, R. G.; White, S.; Roddick, D. M. Organometallics 1998, 17, 4493-4499. (c) Edelbach, B. L.; Lachichotte, R. J.; Jones, W. D. J. Am. Chem. Soc. 1998, 120, 2843-2853. See also ref 12.
47. Konze, W. V.; Scott, B. L.; Kubas, G. J. J. Am. Chem. Soc. 2002, 124, 12 550-12 556.
48. Tellers, D. M.; Yung, C. M.; Amdtsen, B. A.; Adamson, D. R.; Bergman, R. G. J. Am. Chem. Soc. 2002, 124, 1400-1410.
49. (a) Appleton, T. G.; Bennett. M. A.; Tomkins, I 1. B. J. Chem Chern. Soc., Dalton Trans. 1976, 439-446.
50. (b) Smith, Jr., D. C.; Haar, C. M.; Stevens, E. D.; Nolan, S. P.; Marshall, W., J.; Moloy, K. G. Organometallics 2000, 19, 1427-1433.
51. Jutzi, P.; Müller, C.; Stammler, A.; Stammler, H.-G. Organometallics 2000, 19, 1442-1444.
52. (a) Romeo, R.; Scolaro, L. M.; Pluntio, M. R.; Del Zotto, A. Transition Met. Chem. 1998, 23, 789-793.
53. (b) Alibrandi, G.; Bruno, G.: Lanza, S.; Minniti, D.; Romeo, R.; Tobe, M. L. Inorg. Chem. 1987, 26, 185-190.
54. Smith, D. C., Jr.; Haar, C. M.; Stevens, E. D.; Nolan, S. P.; Marshall, W. J.; Moloy, K. G. Organometallics 2000, 19, 1427-1433.
55. Haar, C. M.; Nolan, S. P.; Marshall, W. J.; Moloy, K. G.; Prock, A.; Giering, W. G. Organometallics 1999, 18, 474-479.
56. Tolman, C. A. J. Am. Chem. Soc. 1970, 92, 2953-2956 and references therein.
57. Thomas, J. C.; Peters, J. C. Inorg. Chem. 2003, in press.
58. Anton, D. R.; Crabtree, R, H. Organometallics 1983, 2, 621-627.
59. Dietsche, W. H. Tetrahedron Lett. 1966, 49, 6187-6191.
60. Morris, G. A.; Freeman, R. J. Magn. Res. 1978, 29, 433-462.
61. Bain, A. D.; Cramer, J. A. J. Magn. Res. 1996, 118, 21-27.
62. Langford, C. H.; Gray, H. B. Ligand Substitution Processes; Benjamin: New York, 1966; pp 18-54.
63. (a) Romeo, R. Comments Inorg. Chem. 1990, 11, 21-57.
64. (b) Romeo, R.; Scolaro, L. M.; Nastasi, N.; Arena, G. Inorg. Chem. 1996, 35, 5087-5096.
65. (c) Romeo, R.; Alibrandi, G. Inorg. Chem. 1997, 36, 4822-4830.
66. (d) Romeo, R.; Plutino, M. R.; Elding, L. I. Inorg. Chem. 1997, 36, 5909-5916.
67. (e) Plutino, M. R.; Scolaro, L. M.; Romeo, R.; Grassi, A. Inorg. Chem. 2000, 39, 2712-2720.
68. The results of an X-ray diffraction study of 19 are contained in the Supporting Information.
69. Fernandez, A. L.; Wilson, M. R.; Prock, A.; Giering, W. P. Organometallics 2001, 20, 3429-3435.
70. Puddephatt, R. J. Coord. Chem. Rev. 2001. 219-221, 157-185.
71. For examples of 5-coordinate platinum(IV): (a) Ulrich, F.; Kaminsky, W.; Goldberg, K. I. J. Am. Chem. Soc. 2001, 123, 6423-6424. (b) Ulrich, F.; Goldberg, K. I. J. Am. Chem. Soc. 2002. 124, 6804-6805. (c) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 124, 6425-6426. For lead references on 6-coordinate platinum(IV): (d) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M, Advanced Inorganic Chemistry, 6th ed.; John Wiley & Sons: New York, 1999; pp 1080-1082. (e) Roundhill, D. M. In Comprehensive Coordination Chemistry, Vol. 5: Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, 1987; pp 353-531.
72. For examples of 5-coordinate platinum(IV): (a) Ulrich, F.; Kaminsky, W.; Goldberg, K. I. J. Am. Chem. Soc. 2001, 123, 6423-6424. (b) Ulrich, F.; Goldberg, K. I. J. Am. Chem. Soc. 2002. 124, 6804-6805. (c) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 124, 6425-6426. For lead references on 6-coordinate platinum(IV): (d) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M, Advanced Inorganic Chemistry, 6th ed.; John Wiley & Sons: New York, 1999; pp 1080-1082. (e) Roundhill, D. M. In Comprehensive Coordination Chemistry, Vol. 5: Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, 1987; pp 353-531.
73. For examples of 5-coordinate platinum(IV): (a) Ulrich, F.; Kaminsky, W.; Goldberg, K. I. J. Am. Chem. Soc. 2001, 123, 6423-6424. (b) Ulrich, F.; Goldberg, K. I. J. Am. Chem. Soc. 2002. 124, 6804-6805. (c) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 124, 6425-6426. For lead references on 6-coordinate platinum(IV): (d) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M, Advanced Inorganic Chemistry, 6th ed.; John Wiley & Sons: New York, 1999; pp 1080-1082. (e) Roundhill, D. M. In Comprehensive Coordination Chemistry, Vol. 5: Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, 1987; pp 353-531.
74. For examples of 5-coordinate platinum(IV): (a) Ulrich, F.; Kaminsky, W.; Goldberg, K. I. J. Am. Chem. Soc. 2001, 123, 6423-6424. (b) Ulrich, F.; Goldberg, K. I. J. Am. Chem. Soc. 2002. 124, 6804-6805. (c) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 124, 6425-6426. For lead references on 6-coordinate platinum(IV): (d) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M, Advanced Inorganic Chemistry, 6th ed.; John Wiley & Sons: New York, 1999; pp 1080-1082. (e) Roundhill, D. M. In Comprehensive Coordination Chemistry, Vol. 5: Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, 1987; pp 353-531.
75. For examples of 5-coordinate platinum(IV): (a) Ulrich, F.; Kaminsky, W.; Goldberg, K. I. J. Am. Chem. Soc. 2001, 123, 6423-6424. (b) Ulrich, F.; Goldberg, K. I. J. Am. Chem. Soc. 2002. 124, 6804-6805. (c) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 124, 6425-6426. For lead references on 6-coordinate platinum(IV): (d) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M, Advanced Inorganic Chemistry, 6th ed.; John Wiley & Sons: New York, 1999; pp 1080-1082. (e) Roundhill, D. M. In Comprehensive Coordination Chemistry, Vol. 5: Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, 1987; pp 353-531.
76. Nozaki, K.; Sato, N.; Tonomura, Y.; Yasutomi, M.; Takaya, H.; Hiyama, T.; Matsubara, T.; Koga, N. J. Am. Chem. Soc. 1997, 119, 12 779-12 795.
77. 3 has been prepared and is thermally very robust. J. C. Thomas, J. C. Peters, unpublished results.
78. Clark, H. C.; Manzer, L. E. J. Organomet. Chem. 1973, 59, 411-428.
79. Costa, E.; Pringle, P. G.; Ravetz, M. Inorg. Synth. 1995, 31, 284-286.
80. Hackett, M.; Whitesides, G. M. Organometallics 1987, 6, 403-410.
81. Appleton, T. G.; Bennett, M. A. Inorg. Chem. 1978, 17, 738-747.
82. Seyferth, D.; Burlitch, J. M. J. Org. Chem. 1963, 28, 2463.
83. Schore, N. E.; Benner, L. S.; Labelle, B. E. Inorg. Chem. 1981, 20, 3200-3208.
84. Blicke, F. F.; Hotelling, E. B. J. Am. Chem. Soc. 1954, 76, 5099-5103.
85. Stehling, U. M.; Stein, K. M.; Kesti, M. R.; Waymouth, R. M. Macromolecules 1998, 31, 2019-2027.
86. LeSuer, R. J.; Geiger, W. E. Angew. Chem., Int. Ed. 2000, 39, 248-250.
87. Kemmitt, R. D. W.; Nichols, D. I.; Peacock, R. D. J. Chem. Soc. A 1968, 2149-2152.
88. Bakshi, P. K.; Linden, A.; Vincent, B. R.; Roe, S. P.; Adhikesavalu, D.; Cameron, T. S.; Knop, O. Can. J. Chem. 1994, 72, 1273-1293.
89. Crystallographic data have been deposited at the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, and copies can be obtained on request, free of charge, by quoting the publication citation and the deposition number 151640 (7), 198492 (8-toluene), 198491 (9), 156632 (13-2THF), 186231 (19-4(o-xylene)), 198490 (25-benzene).