Diastereoselectivity of Borane Addition to Chiral Triquinphosphoranes. NMR, X-ray, and Molecular Modeling Studies

Organometallics

Volumn 18, Issue 5, 1999, Pages 915-927

  Marchi, Caroline ^a   Fotiadu, Frédéric ^a   Buono, Gérard ^a  

^a AIX MARSEILLE UNIVERSITY   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000318963     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980774c     Document Type: Article

References (116)

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16. (c) For a review on spirophosphoranes and polycyclic phosphoranes with a PH bond see: Burgada, R.; Setton, R. In The Chemistry of Organophosphorus Compounds; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1994; Vol. 3, pp 185-272.
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29. It is worth noting that Hellwinkel isolated the first optically active pentaarylphosphorane. However, it undergoes stereoisomerization with low conversion energy barriers: Hellwinkel, D. Chem. Ber. 1966, 99, 3642.
30. (a) Klaebe, A.; Brazier, J. F.; Guarrigues, B.; Wolf, R.; Stefanovsky, Y. Phosphorus Sulfur Relat. Elem. 1981, 10, 53.
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35. Spirophosphoranes have been recently applied with success in Wittig type reactions. These spirophosphoranes were prepared from the corresponding P-H spirophosphoranes by alkylation: (a) Bojin, M. L.; Barkallha, S.; Evans, S. A., Jr. J. Am. Chem. Soc. 1996, 118, 1549. (b) Kojima, S.; Takagi, R. Akiba, K.-y. J. Am. Chem. Soc. 1997, 119, 5970. Burger, K. Pentacoordinated Phosphorus in Synthesis. In Organophosphorus Reagents in Organic Synthesis; Cadogan, J. I. G., Ed.; Academic Press: New York, 1979; pp 467-510. For the free radical alkylthiylation of hydridophosphorane 5, see: Bentrude, W. G.; Kawashima, T.; Keys, B. A.; Garroussian, M.; Heide, W.; Wedegaertner, D. A. J. Am. Chem. Soc. 1987, 109, 1227. (e) Chiral triquinphosphoranes were shown to undergo UV-light-induced alkylthiylation reactions by a series of alkyl disulfides to give the corresponding isolable thia chiral triquinphosphoranes: Unpublished results.
36. Spirophosphoranes have been recently applied with success in Wittig type reactions. These spirophosphoranes were prepared from the corresponding P-H spirophosphoranes by alkylation: (a) Bojin, M. L.; Barkallha, S.; Evans, S. A., Jr. J. Am. Chem. Soc. 1996, 118, 1549. (b) Kojima, S.; Takagi, R. Akiba, K.-y. J. Am. Chem. Soc. 1997, 119, 5970. Burger, K. Pentacoordinated Phosphorus in Synthesis. In Organophosphorus Reagents in Organic Synthesis; Cadogan, J. I. G., Ed.; Academic Press: New York, 1979; pp 467-510. For the free radical alkylthiylation of hydridophosphorane 5, see: Bentrude, W. G.; Kawashima, T.; Keys, B. A.; Garroussian, M.; Heide, W.; Wedegaertner, D. A. J. Am. Chem. Soc. 1987, 109, 1227. (e) Chiral triquinphosphoranes were shown to undergo UV-light-induced alkylthiylation reactions by a series of alkyl disulfides to give the corresponding isolable thia chiral triquinphosphoranes: Unpublished results.
37. Spirophosphoranes have been recently applied with success in Wittig type reactions. These spirophosphoranes were prepared from the corresponding P-H spirophosphoranes by alkylation: (a) Bojin, M. L.; Barkallha, S.; Evans, S. A., Jr. J. Am. Chem. Soc. 1996, 118, 1549. (b) Kojima, S.; Takagi, R. Akiba, K.-y. J. Am. Chem. Soc. 1997, 119, 5970. Burger, K. Pentacoordinated Phosphorus in Synthesis. In Organophosphorus Reagents in Organic Synthesis; Cadogan, J. I. G., Ed.; Academic Press: New York, 1979; pp 467-510. For the free radical alkylthiylation of hydridophosphorane 5, see: Bentrude, W. G.; Kawashima, T.; Keys, B. A.; Garroussian, M.; Heide, W.; Wedegaertner, D. A. J. Am. Chem. Soc. 1987, 109, 1227. (e) Chiral triquinphosphoranes were shown to undergo UV-light-induced alkylthiylation reactions by a series of alkyl disulfides to give the corresponding isolable thia chiral triquinphosphoranes: Unpublished results.
38. Spirophosphoranes have been recently applied with success in Wittig type reactions. These spirophosphoranes were prepared from the corresponding P-H spirophosphoranes by alkylation: (a) Bojin, M. L.; Barkallha, S.; Evans, S. A., Jr. J. Am. Chem. Soc. 1996, 118, 1549. (b) Kojima, S.; Takagi, R. Akiba, K.-y. J. Am. Chem. Soc. 1997, 119, 5970. Burger, K. Pentacoordinated Phosphorus in Synthesis. In Organophosphorus Reagents in Organic Synthesis; Cadogan, J. I. G., Ed.; Academic Press: New York, 1979; pp 467-510. For the free radical alkylthiylation of hydridophosphorane 5, see: Bentrude, W. G.; Kawashima, T.; Keys, B. A.; Garroussian, M.; Heide, W.; Wedegaertner, D. A. J. Am. Chem. Soc. 1987, 109, 1227. (e) Chiral triquinphosphoranes were shown to undergo UV-light-induced alkylthiylation reactions by a series of alkyl disulfides to give the corresponding isolable thia chiral triquinphosphoranes: Unpublished results.
39. Spirophosphoranes have been recently applied with success in Wittig type reactions. These spirophosphoranes were prepared from the corresponding P-H spirophosphoranes by alkylation: (a) Bojin, M. L.; Barkallha, S.; Evans, S. A., Jr. J. Am. Chem. Soc. 1996, 118, 1549. (b) Kojima, S.; Takagi, R. Akiba, K.-y. J. Am. Chem. Soc. 1997, 119, 5970. Burger, K. Pentacoordinated Phosphorus in Synthesis. In Organophosphorus Reagents in Organic Synthesis; Cadogan, J. I. G., Ed.; Academic Press: New York, 1979; pp 467-510. For the free radical alkylthiylation of hydridophosphorane 5, see: Bentrude, W. G.; Kawashima, T.; Keys, B. A.; Garroussian, M.; Heide, W.; Wedegaertner, D. A. J. Am. Chem. Soc. 1987, 109, 1227. (e) Chiral triquinphosphoranes were shown to undergo UV-light-induced alkylthiylation reactions by a series of alkyl disulfides to give the corresponding isolable thia chiral triquinphosphoranes: Unpublished results.
40. Vannoorenberghe, Y.; Buono, G. J. Am. Chem. Soc. 1990, 112, 6142.
41. N,N'-Bis(1-alkyl-2-hydroxyethyl)ethylenediamine: diamino diols 7-12.
42. N,N'-Bis(2-hydroxyethyl)-1,2-dialkylethylene-1,2-diamine: diamino diols 19 and 20.
43. N,N'-Bis(2-alkyl-2-hydroxyethyl)ethylenediamine: diamino diol 23.
44. The N-X-L nomenclature system has been previously described: N valence electrons about an atomic center X with L ligands: Perkins, C. W.; Martin, J. C.; Arduengo, A. J., III; Lau, W.; Algeria, A.; Kochi, J. K. J. Am. Chem. Soc. 1980, 102, 7753.
45. (a) Tebby, J. C. In Methods in Stereochemical Analysis: Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis; Verkade, J. G., Quin, D. L., Eds.; VCH: Deerfield Beach, FL, 1987; Vol. 8, p 40. (b) Tebby, J. C. Handbook of Phosphorus 31 Nuclear Magnetic Resonance Data; CRC Press: Boca Raton, FL, 1991. Gallagher, M. J. In Phosphorus-31 NMR Spectral Properties in Compound Characterization and Structural Analysis; Quin, D. L , Verkade, J. G., Eds.; VCH: New York, 1994; Chapter 29, pp 385-393.
46. (a) Tebby, J. C. In Methods in Stereochemical Analysis: Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis; Verkade, J. G., Quin, D. L., Eds.; VCH: Deerfield Beach, FL, 1987; Vol. 8, p 40. (b) Tebby, J. C. Handbook of Phosphorus 31 Nuclear Magnetic Resonance Data; CRC Press: Boca Raton, FL, 1991. Gallagher, M. J. In Phosphorus-31 NMR Spectral Properties in Compound Characterization and Structural Analysis; Quin, D. L , Verkade, J. G., Eds.; VCH: New York, 1994; Chapter 29, pp 385-393.
47. (a) Tebby, J. C. In Methods in Stereochemical Analysis: Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis; Verkade, J. G., Quin, D. L., Eds.; VCH: Deerfield Beach, FL, 1987; Vol. 8, p 40. (b) Tebby, J. C. Handbook of Phosphorus 31 Nuclear Magnetic Resonance Data; CRC Press: Boca Raton, FL, 1991. Gallagher, M. J. In Phosphorus-31 NMR Spectral Properties in Compound Characterization and Structural Analysis; Quin, D. L , Verkade, J. G., Eds.; VCH: New York, 1994; Chapter 29, pp 385-393.
48. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
49. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
50. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
51. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
52. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
53. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
54. Several 10-P-5 hydridophosphoranes are in equilibrium with a 8-P-3 tautomeric structure. It has been found that factors such as temperature, solvent basicity, basicity of the heteroatoms at the binding site, ring size, the presence of an unsaturation in the rings, and the size of the substituents on the ring affect the ratio between the 10-P-5 and the 8-P-3 species: (a) Burgada, R. Bull Soc. Chim. Fr. 1975, 407. (b) Muños, A. Bull. Soc. Chim. Fr. 1977, 728. Burgada, R.; Laurenço, C. J. Organomet. Chem. 1974, 66, 255. Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 4333. (e) Atkins, T. J.; Richman, J. E. Tetrahedron Lett. 1978, 5149. (f) Houalla, D.; Sanchez, M.; Gonbeau, D.; Pfister-Guillouzo, G. Nouv: J. Chem. 1979, 8-9, 507. (g) Houalla, D.; Brazier, J. F.; Sanchez, M.; Wolf, R. Tetrahedron Lett. 1972, 2969.
55. (a) Berry, R. S. J. Chem. Phys. 1960, 32, 933. (b) Mislow, K. Acc. Chem. Res. 1970, 5, 321. The turnstile mechanism is sometimes alternatively invoked, but for the triquinphosphoranes the pseudorotation according to Berry is by far the most appropriated in the sense of symmetrical factors and is due to the structural dependence of five-membered rings: Ugi, I.; Marquarding, D.; Klusacek, H.; Gillespie, P.; Ramirez, F. Acc. Chem. Res. 1971, 4, 288. The topological equivalence between Berry and turnstile pseudorotations has been addressed: Russeger, P.; Brickmann, J. Chem. Phys. Lett. 1975, 30, 276.
56. (a) Berry, R. S. J. Chem. Phys. 1960, 32, 933. (b) Mislow, K. Acc. Chem. Res. 1970, 5, 321. The turnstile mechanism is sometimes alternatively invoked, but for the triquinphosphoranes the pseudorotation according to Berry is by far the most appropriated in the sense of symmetrical factors and is due to the structural dependence of five-membered rings: Ugi, I.; Marquarding, D.; Klusacek, H.; Gillespie, P.; Ramirez, F. Acc. Chem. Res. 1971, 4, 288. The topological equivalence between Berry and turnstile pseudorotations has been addressed: Russeger, P.; Brickmann, J. Chem. Phys. Lett. 1975, 30, 276.
57. (a) Berry, R. S. J. Chem. Phys. 1960, 32, 933. (b) Mislow, K. Acc. Chem. Res. 1970, 5, 321. The turnstile mechanism is sometimes alternatively invoked, but for the triquinphosphoranes the pseudorotation according to Berry is by far the most appropriated in the sense of symmetrical factors and is due to the structural dependence of five-membered rings: Ugi, I.; Marquarding, D.; Klusacek, H.; Gillespie, P.; Ramirez, F. Acc. Chem. Res. 1971, 4, 288. The topological equivalence between Berry and turnstile pseudorotations has been addressed: Russeger, P.; Brickmann, J. Chem. Phys. Lett. 1975, 30, 276.
58. (a) Berry, R. S. J. Chem. Phys. 1960, 32, 933. (b) Mislow, K. Acc. Chem. Res. 1970, 5, 321. The turnstile mechanism is sometimes alternatively invoked, but for the triquinphosphoranes the pseudorotation according to Berry is by far the most appropriated in the sense of symmetrical factors and is due to the structural dependence of five-membered rings: Ugi, I.; Marquarding, D.; Klusacek, H.; Gillespie, P.; Ramirez, F. Acc. Chem. Res. 1971, 4, 288. The topological equivalence between Berry and turnstile pseudorotations has been addressed: Russeger, P.; Brickmann, J. Chem. Phys. Lett. 1975, 30, 276.
59. For the nomenclature of chiral pentacoordinate compounds see: Martin, J. C.; Balthazor, T. M. J. Am. Chem. Soc. 1977, 99, 152. "The sense of chirality can be specified by viewing the idealized TBP structure along its axial axis in the orientation which places nearer the viewer that axial substituent which has the higher priority rank in the CIP nomenclature scheme. The priority ranking of the equatorial ligands using the CIP conventions results in order of decreasing priority which can be recognized by the viewer as being clockwise (R) or counterclockwise (S)."
60. According to Holmes' empirical calculations the energy difference between the TBP and the SP structures should be 2.0 ± 1.5 kcal/ mol in favor of the former, supporting a fast pseudorotation process at room temperature: Holmes, R. R. J. Am. Chem. Sac. 1978, 100, 433.
61. It is well-known that a phosphorane bearing oxygen and nitrogen substituents preferentially has oxygen atoms in the axial positions as the most stable stereoisomer according to the apicophilicity of the elements: Trippett, S. Phosphorus Sulfur Relat. Elem. 1976, 1, 89.
62. Holmes, R. R. Pentacoordinated Phosphorus; ACS Monograph Series 175 and 176; American Chemical Society: Washington, DC, 1980; Vols. 1 and 2.
63. (a) McDowell, S.; Streitwieser, A. J. Am. Chem. Soc. 1986, 107, 5849. (b) Thatcher, G. R. J.; Kluger, R. In Advances in Physical Organic Chemistry; Bethell, D., Ed.; Academic Press: New York, 1989; Vol. 25. Buono, G.; Llinas, J. R. J. Am. Chem. Soc. 1981, 103, 4532. Wang, P.; Zhang, Y; Glaser, R.; Reed, A. E.; Schleyer, P. v. R.; Streitwieser, A. J. Am. Chem. Soc. 1991, 113, 55. (e) Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272.
64. (a) McDowell, S.; Streitwieser, A. J. Am. Chem. Soc. 1986, 107, 5849. (b) Thatcher, G. R. J.; Kluger, R. In Advances in Physical Organic Chemistry; Bethell, D., Ed.; Academic Press: New York, 1989; Vol. 25. Buono, G.; Llinas, J. R. J. Am. Chem. Soc. 1981, 103, 4532. Wang, P.; Zhang, Y; Glaser, R.; Reed, A. E.; Schleyer, P. v. R.; Streitwieser, A. J. Am. Chem. Soc. 1991, 113, 55. (e) Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272.
65. (a) McDowell, S.; Streitwieser, A. J. Am. Chem. Soc. 1986, 107, 5849. (b) Thatcher, G. R. J.; Kluger, R. In Advances in Physical Organic Chemistry; Bethell, D., Ed.; Academic Press: New York, 1989; Vol. 25. Buono, G.; Llinas, J. R. J. Am. Chem. Soc. 1981, 103, 4532. Wang, P.; Zhang, Y; Glaser, R.; Reed, A. E.; Schleyer, P. v. R.; Streitwieser, A. J. Am. Chem. Soc. 1991, 113, 55. (e) Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272.
66. (a) McDowell, S.; Streitwieser, A. J. Am. Chem. Soc. 1986, 107, 5849. (b) Thatcher, G. R. J.; Kluger, R. In Advances in Physical Organic Chemistry; Bethell, D., Ed.; Academic Press: New York, 1989; Vol. 25. Buono, G.; Llinas, J. R. J. Am. Chem. Soc. 1981, 103, 4532. Wang, P.; Zhang, Y; Glaser, R.; Reed, A. E.; Schleyer, P. v. R.; Streitwieser, A. J. Am. Chem. Soc. 1991, 113, 55. (e) Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272.
67. (a) McDowell, S.; Streitwieser, A. J. Am. Chem. Soc. 1986, 107, 5849. (b) Thatcher, G. R. J.; Kluger, R. In Advances in Physical Organic Chemistry; Bethell, D., Ed.; Academic Press: New York, 1989; Vol. 25. Buono, G.; Llinas, J. R. J. Am. Chem. Soc. 1981, 103, 4532. Wang, P.; Zhang, Y; Glaser, R.; Reed, A. E.; Schleyer, P. v. R.; Streitwieser, A. J. Am. Chem. Soc. 1991, 113, 55. (e) Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272.
68. It is worth noting the unusually strong basic character of a nitrogen atom bound to phosphorus in the case of bicyclic aminophosphanes 8-P-3: Grec, D.; Hubert-Pfalzgraf, L. G.; Riess, J. G.; Grand, A. J. Am. Chem. Soc. 1980, 102, 7134.
69. Holmes, R. R.; Deiters, J. A. J. Am. Chem. Sac. 1977, 99, 3318.
70. Meunier, P. F.; Dieters, J. A.; Holmes, R. R. Inorg. Chem. 1976, 15(10), 2577.
71. This percentage of deformation has been calculated by our team: Llinas, J. R. Thesis, University of Marseilles, 1979.
72. (a) Day, R. O.; Schmidpeter, A.; Holmes, R. R. Inorg. Chem. 1982, 21, 3916. (b) Day, R. O.; Schmidpeter, A.; Holmes, R. R. Inorg. Chem. 1983, 22, 3696.
73. (a) Day, R. O.; Schmidpeter, A.; Holmes, R. R. Inorg. Chem. 1982, 21, 3916. (b) Day, R. O.; Schmidpeter, A.; Holmes, R. R. Inorg. Chem. 1983, 22, 3696.
74. Gilheany, D. G. Chem. Rev. 1994, 94(5), 1339-1374.
75. This P-N bond length is close to the covalent radius. 1.85 Å: Sutton, L., Ed. Tables of Interatomic Distances and Configuration in Molecules and Ions; The Chemical Society: London, 1958 and 1965; Special Publications Nos. 11 and 18.
76. This P-N bond may be compared with the P-N bond in the neutral hexacoordinated phosphorus compounds obtained by Lewis acid-base interactions between pentacoordinated phosphorus compounds and nitrogen donor atom; see Table 2 of: Holmes, R. R. Chem. Rev. 1996, 96, 927. See also Table 2 of: Wong, C. Y.; Kennepohl, D. K.; Cavell, R. G. Chem. Rev. 1996, 96, 1917.
77. This P-N bond may be compared with the P-N bond in the neutral hexacoordinated phosphorus compounds obtained by Lewis acid-base interactions between pentacoordinated phosphorus compounds and nitrogen donor atom; see Table 2 of: Holmes, R. R. Chem. Rev. 1996, 96, 927. See also Table 2 of: Wong, C. Y.; Kennepohl, D. K.; Cavell, R. G. Chem. Rev. 1996, 96, 1917.
78. Clardy, J. C.; Milbrath, D. S.; Springer, J. P.; Verkade, J. G. J. Am. Chem. Soc. 1976, 98, 623.
79. (a) Ramirez, F.; Ugi, I. In Advances in Physical Organic Chemistry; Gold, V., Ed.; Academic Press: New York, 1971; Vol. 9. (b) Ramirez, F.; Ugi, I. Bull. Soc. Chim. Fr. 1974, 453. Ramirez, F.; Pfohl, S.; Tsolig, E. A.; Pilot, J. F.; Smith, C. P.; Ugi, I.; Marquarding, D.; Gillespie, P.; Hoffmann, P. Phosphorus Relat. Group V Elem. 1971, 1, 1.
80. (a) Ramirez, F.; Ugi, I. In Advances in Physical Organic Chemistry; Gold, V., Ed.; Academic Press: New York, 1971; Vol. 9. (b) Ramirez, F.; Ugi, I. Bull. Soc. Chim. Fr. 1974, 453. Ramirez, F.; Pfohl, S.; Tsolig, E. A.; Pilot, J. F.; Smith, C. P.; Ugi, I.; Marquarding, D.; Gillespie, P.; Hoffmann, P. Phosphorus Relat. Group V Elem. 1971, 1, 1.
81. (a) Ramirez, F.; Ugi, I. In Advances in Physical Organic Chemistry; Gold, V., Ed.; Academic Press: New York, 1971; Vol. 9. (b) Ramirez, F.; Ugi, I. Bull. Soc. Chim. Fr. 1974, 453. Ramirez, F.; Pfohl, S.; Tsolig, E. A.; Pilot, J. F.; Smith, C. P.; Ugi, I.; Marquarding, D.; Gillespie, P.; Hoffmann, P. Phosphorus Relat. Group V Elem. 1971, 1, 1.
82. (a) Andrionov, V. I.; Atovmyan, L. O.; Golovina, N. I.; Klitskaya, G. A. Zh. Strukt. Khim. 1967, 8, 303. (b) Cassoux, P.; Kuczkowski, R. L.; Brian, P. S.; Taylor, R. C. Inorg. Chem. 1975, 14, 126. Colquhoun, H. M.; Jones, G.; Maud, J. M.; Stoddart, J. F.; Williams, D. J. J. Chem. Soc., Dalton Trans. 1984, 63.
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85. Despite numerous attempts, we could not obtain any crystals of solid phosphoranes 17 and 18 suitable for X-ray diffraction.
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89. (a) Shih, S. K.; Peyerimhoff, S. D. J. Chem. Soc., Faraday Trans. 1879, 75(2). 379. (b) Trinquier, G.; Daudey, J.-P., Caruana, G.; Madaule, Y. J. Am. Chem. Soc. 1984, 106, 4794. Reed, A. E.; Schleyer, P. v. R. Chem. Phys. Lett. 1987, 133, 553. Ewig, C. S.; Van Wazer, J. R. J. Am. Chem. Soc. 1989, 111, 1552. (e) Wang, P.; Agrafiotis, D. K.; Streitwieser, A.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1990, 201. (f) Ding, F.-J.; Zhang, L.-F. Int. J. Quantum Chem. 1996, 60, 1037.
90. (a) Shih, S. K.; Peyerimhoff, S. D. J. Chem. Soc., Faraday Trans. 1879, 75(2). 379. (b) Trinquier, G.; Daudey, J.-P., Caruana, G.; Madaule, Y. J. Am. Chem. Soc. 1984, 106, 4794. Reed, A. E.; Schleyer, P. v. R. Chem. Phys. Lett. 1987, 133, 553. Ewig, C. S.; Van Wazer, J. R. J. Am. Chem. Soc. 1989, 111, 1552. (e) Wang, P.; Agrafiotis, D. K.; Streitwieser, A.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1990, 201. (f) Ding, F.-J.; Zhang, L.-F. Int. J. Quantum Chem. 1996, 60, 1037.
91. (a) Shih, S. K.; Peyerimhoff, S. D. J. Chem. Soc., Faraday Trans. 1879, 75(2). 379. (b) Trinquier, G.; Daudey, J.-P., Caruana, G.; Madaule, Y. J. Am. Chem. Soc. 1984, 106, 4794. Reed, A. E.; Schleyer, P. v. R. Chem. Phys. Lett. 1987, 133, 553. Ewig, C. S.; Van Wazer, J. R. J. Am. Chem. Soc. 1989, 111, 1552. (e) Wang, P.; Agrafiotis, D. K.; Streitwieser, A.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1990, 201. (f) Ding, F.-J.; Zhang, L.-F. Int. J. Quantum Chem. 1996, 60, 1037.
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104. These values should be compared with the sum of experimental bond angles around axial and equatorial nitrogen atoms in cyclen-phosphorane, which are 348 and 356°, respectively: Lattman, M.; Olmstead, M. M.; Power, P. P.; Rankin, D. W. H.; Robertson, H. E. Inorg. Chem. 1988, 27, 3012.
105. Torsion angles changed from -180 to 180° for isopropyl groups and from 0 to 180° for phenyl substituents
106. (a) Curtin, D. Y. Rec. Chem. Prog. 1954, 15, 111. (b) Seeman, J. I. Chem. Rev. 1983, 83, 83. Seeman, J. I. J. Chem. Educ. 1986, 63, 42.
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109. ax bond is scarcely reduced. These disappointing observations show that rather elaborate theoretical methods will be needed to describe these intriguing compounds properly. The use of the semiempirical AM1 approach therefore seems to be particularly appropriate for the present compounds, even if the reasons why it should be more successful than SCF or B3LYP techniques are not immediately apparent."
110. 3 group in an axial position, whereas we demonstrate here that this reaction proceeds only on the axial nitrogen atom and obeys the Curtin-Hammett principle. Taken together, these data strongly support our own conclusions and validate the results of AM1 calculations on the free triquinphosphoranes.
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