Restricted Rotation around the P-C Bond in Metalated Phosphonium Salts: A Variable-Temperature 1H NMR Study. X-ray Crystal Structures of [{AuP(C6H11)3}2{μ-C(PTo 3)(py-2)}]ClO4 and [(AuPPh3)2 {μ-{C(PPh3)(py-2)}(AuPPh3)}](CF3SO 3)2

José Vicente; María Teresa Chicote; María Cristina Lagunas; Peter G. Jones; Birte Ahrens

Restricted Rotation around the P-C Bond in Metalated Phosphonium Salts: A Variable-Temperature ¹H NMR Study. X-ray Crystal Structures of [{AuP(C₆H₁₁)₃}₂{μ-C(PTo ₃)(py-2)}]ClO₄ and [(AuPPh₃)₂ {μ-{C(PPh₃)(py-2)}(AuPPh₃)}](CF₃SO ₃)₂

José Vicente^*, María Teresa Chicote, María Cristina Lagunas, Peter G. Jones, Birte Ahrens

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

28 Citations (Scopus)

Abstract

A variable-temperature ¹H NMR study has been performed for the complexes [(AuL)₂{μ-C(PTo₃)R}]ClO₄ [To = C₆H₄Me-4; L = PPh₃, R = C(O)NMe₂, pyridyl-2 (py-2), C(O)Ph, C(O)C₆H₄OMe-4, C(O)C₆H₄NO₂-4, CO₂Me, CN; R = py-2, L = P(C₆H₄OMe-4)₃, P(C₆H₁₁)₃, PMe₃], [(AuPPh₃)₂{μ₂-{C(PTo ₃(py-2)}{Ag(η²O₂-NO)(OC1O ₃)}]-H₂O, and [(AuPPh₃)₂{μ₂-{C(PTo ₃)(py-2)}(AuPPh₃)}](ClO₄)₂. The To₃P-C(AuL)₂ rotation is shown to be restricted at room or lower temperatures. The estimated values of δG*for these processes lie in the range 67.3-42.2 kJ-mol^-1 and are attributed mainly to steric effects, although electronic effects could also be operative. The crystal structures of [{AuP(C₆H₁₁,)₃}₂{μ-C(PTo ₃)(py-2)}]ClO₄ (2c) and [(AuPPh₃)₂{μHC(PPh₃)(py-2)}(AuPPh ₃)}](CF₃SO₃)₂ (9′-2CH₂Cl₂) have been determined. 2c crystallizes in the monoclinic system, space group P2₁/n, with a = 14.056(3) Å, b = 24.556(4) Å, c = 19.110(3) Å, β= 111.00(2)° and, Z = 4. 9′ crystallizes in the monoclinic system, space group P2_/c, with a = 17.232(6) Å, b = 25.800(7), c = 18.005(7) Å, β= 96.77(3)°, and Z = 4.

Original language	English
Pages (from-to)	4938-4944
Number of pages	7
Journal	Inorganic Chemistry
Volume	36
Issue number	22
Publication status	Published - 01 Dec 1997
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Vicente, José ; Chicote, María Teresa ; Lagunas, María Cristina et al. / Restricted Rotation around the P-C Bond in Metalated Phosphonium Salts : A Variable-Temperature ¹H NMR Study. X-ray Crystal Structures of [{AuP(C₆H₁₁)₃}₂{μ-C(PTo ₃)(py-2)}]ClO₄ and [(AuPPh₃)₂ {μ-{C(PPh₃)(py-2)}(AuPPh₃)}](CF₃SO ₃)₂. In: Inorganic Chemistry. 1997 ; Vol. 36, No. 22. pp. 4938-4944.

@article{2ae9368ec81f44178b53c952d2c13447,

title = "Restricted Rotation around the P-C Bond in Metalated Phosphonium Salts: A Variable-Temperature 1H NMR Study. X-ray Crystal Structures of [{AuP(C6H11)3}2{μ-C(PTo 3)(py-2)}]ClO4 and [(AuPPh3)2 {μ-{C(PPh3)(py-2)}(AuPPh3)}](CF3SO 3)2",

abstract = "A variable-temperature 1H NMR study has been performed for the complexes [(AuL)2{μ-C(PTo3)R}]ClO4 [To = C6H4Me-4; L = PPh3, R = C(O)NMe2, pyridyl-2 (py-2), C(O)Ph, C(O)C6H4OMe-4, C(O)C6H4NO2-4, CO2Me, CN; R = py-2, L = P(C6H4OMe-4)3, P(C6H11)3, PMe3], [(AuPPh3)2{μ2-{C(PTo 3(py-2)}{Ag(η2O2-NO)(OC1O 3)}]-H2O, and [(AuPPh3)2{μ2-{C(PTo 3)(py-2)}(AuPPh3)}](ClO4)2. The To3P-C(AuL)2 rotation is shown to be restricted at room or lower temperatures. The estimated values of δG*for these processes lie in the range 67.3-42.2 kJ-mol-1 and are attributed mainly to steric effects, although electronic effects could also be operative. The crystal structures of [{AuP(C6H11,)3}2{μ-C(PTo 3)(py-2)}]ClO4 (2c) and [(AuPPh3)2{μHC(PPh3)(py-2)}(AuPPh 3)}](CF3SO3)2 (9′-2CH2Cl2) have been determined. 2c crystallizes in the monoclinic system, space group P21/n, with a = 14.056(3) {\AA}, b = 24.556(4) {\AA}, c = 19.110(3) {\AA}, β= 111.00(2)° and, Z = 4. 9′ crystallizes in the monoclinic system, space group P2/c, with a = 17.232(6) {\AA}, b = 25.800(7), c = 18.005(7) {\AA}, β= 96.77(3)°, and Z = 4.",

author = "Jos{\'e} Vicente and Chicote, {Mar{\'i}a Teresa} and Lagunas, {Mar{\'i}a Cristina} and Jones, {Peter G.} and Birte Ahrens",

year = "1997",

month = dec,

day = "1",

language = "English",

volume = "36",

pages = "4938--4944",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

}

Restricted Rotation around the P-C Bond in Metalated Phosphonium Salts: A Variable-Temperature ¹H NMR Study. X-ray Crystal Structures of [{AuP(C₆H₁₁)₃}₂{μ-C(PTo ₃)(py-2)}]ClO₄ and [(AuPPh₃)₂ {μ-{C(PPh₃)(py-2)}(AuPPh₃)}](CF₃SO ₃)₂. / Vicente, José; Chicote, María Teresa; Lagunas, María Cristina et al.
In: Inorganic Chemistry, Vol. 36, No. 22, 01.12.1997, p. 4938-4944.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Restricted Rotation around the P-C Bond in Metalated Phosphonium Salts

T2 - A Variable-Temperature 1H NMR Study. X-ray Crystal Structures of [{AuP(C6H11)3}2{μ-C(PTo 3)(py-2)}]ClO4 and [(AuPPh3)2 {μ-{C(PPh3)(py-2)}(AuPPh3)}](CF3SO 3)2

AU - Vicente, José

AU - Chicote, María Teresa

AU - Lagunas, María Cristina

AU - Jones, Peter G.

AU - Ahrens, Birte

PY - 1997/12/1

Y1 - 1997/12/1

N2 - A variable-temperature 1H NMR study has been performed for the complexes [(AuL)2{μ-C(PTo3)R}]ClO4 [To = C6H4Me-4; L = PPh3, R = C(O)NMe2, pyridyl-2 (py-2), C(O)Ph, C(O)C6H4OMe-4, C(O)C6H4NO2-4, CO2Me, CN; R = py-2, L = P(C6H4OMe-4)3, P(C6H11)3, PMe3], [(AuPPh3)2{μ2-{C(PTo 3(py-2)}{Ag(η2O2-NO)(OC1O 3)}]-H2O, and [(AuPPh3)2{μ2-{C(PTo 3)(py-2)}(AuPPh3)}](ClO4)2. The To3P-C(AuL)2 rotation is shown to be restricted at room or lower temperatures. The estimated values of δG*for these processes lie in the range 67.3-42.2 kJ-mol-1 and are attributed mainly to steric effects, although electronic effects could also be operative. The crystal structures of [{AuP(C6H11,)3}2{μ-C(PTo 3)(py-2)}]ClO4 (2c) and [(AuPPh3)2{μHC(PPh3)(py-2)}(AuPPh 3)}](CF3SO3)2 (9′-2CH2Cl2) have been determined. 2c crystallizes in the monoclinic system, space group P21/n, with a = 14.056(3) Å, b = 24.556(4) Å, c = 19.110(3) Å, β= 111.00(2)° and, Z = 4. 9′ crystallizes in the monoclinic system, space group P2/c, with a = 17.232(6) Å, b = 25.800(7), c = 18.005(7) Å, β= 96.77(3)°, and Z = 4.

AB - A variable-temperature 1H NMR study has been performed for the complexes [(AuL)2{μ-C(PTo3)R}]ClO4 [To = C6H4Me-4; L = PPh3, R = C(O)NMe2, pyridyl-2 (py-2), C(O)Ph, C(O)C6H4OMe-4, C(O)C6H4NO2-4, CO2Me, CN; R = py-2, L = P(C6H4OMe-4)3, P(C6H11)3, PMe3], [(AuPPh3)2{μ2-{C(PTo 3(py-2)}{Ag(η2O2-NO)(OC1O 3)}]-H2O, and [(AuPPh3)2{μ2-{C(PTo 3)(py-2)}(AuPPh3)}](ClO4)2. The To3P-C(AuL)2 rotation is shown to be restricted at room or lower temperatures. The estimated values of δG*for these processes lie in the range 67.3-42.2 kJ-mol-1 and are attributed mainly to steric effects, although electronic effects could also be operative. The crystal structures of [{AuP(C6H11,)3}2{μ-C(PTo 3)(py-2)}]ClO4 (2c) and [(AuPPh3)2{μHC(PPh3)(py-2)}(AuPPh 3)}](CF3SO3)2 (9′-2CH2Cl2) have been determined. 2c crystallizes in the monoclinic system, space group P21/n, with a = 14.056(3) Å, b = 24.556(4) Å, c = 19.110(3) Å, β= 111.00(2)° and, Z = 4. 9′ crystallizes in the monoclinic system, space group P2/c, with a = 17.232(6) Å, b = 25.800(7), c = 18.005(7) Å, β= 96.77(3)°, and Z = 4.

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M3 - Article

AN - SCOPUS:0000590586

SN - 0020-1669

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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