Restricted Rotation around the P−C Bond in Metalated Phosphonium Salts: A Variable-Temperature <sup>1</sup>H NMR Study. X-ray Crystal Structures of [{AuP(C<sub>6</sub>H<sub>11</sub>)<sub>3</sub>}<sub>2</sub>{μ-C(PTo<sub>3</sub>)(py-2)}]ClO<sub>4</sub> and [(AuPPh<sub>3</sub>)<sub>2</sub>{μ-{C(PPh<sub>3</sub>)(py-2)}(AuPPh<sub>3</sub>)}](CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>
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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(PTo3)(py-2)}{Ag(η2-O2NO)(OClO3)}]·H2O, and [(AuPPh3)2{μ2-{C(PTo3)(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(PTo3)(py-2)}]ClO4 (2c) and [(AuPPh3)2{μ-{C(PPh3)(py-2)}(AuPPh3)}](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 P21/c, with a = 17.232(6) Å, b = 25.800(7), c = 18.005(7) Å, β = 96.77(3)°, and Z = 4.
