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 journalArticle

25 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)22-{C(PTo 3(py-2)}{Ag(η2O2-NO)(OC1O 3)}]-H2O, and [(AuPPh3)22-{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 languageEnglish
Pages (from-to)4938-4944
Number of pages7
JournalInorganic Chemistry
Volume36
Issue number22
Publication statusPublished - 01 Dec 1997
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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