New Neutral and Anionic Alkynylgold(I) Complexes via New Synthetic Methods. Crystal and Molecular Structures of [(PPh 3 ) 2 N][Au(C⋮CCH 2 OH) 2 ], [Au(C⋮CSiMe 3 )(CN t Bu)], and [Au(C⋮CR)PR‘ 3 ] (R‘ = Cyclohexyl, R = CH 2 Cl, CH 2 Br; R‘ = Ph, R = SiMe 3 , t Bu)

[(PPh 3 ) 2 N][Au(acac) 2 ] (acac = acetylacetonate) reacts with terminal alkynes RC⋮CH to give [(PPh 3 ) 2 N][Au(C⋮CR) 2 ] (R = H, t Bu, SiMe 3, CH 2 X (X = Cl, Br, OH)) complexes. The reactions between [(PPh 3 ) 2 N][Au(C⋮CH) 2 ] and [(PPh 3 ) 2 N][AuX 2 ] (X = Cl, Br, I) give [(PPh 3 ) 2 N][Au(C⋮CH)X] complexes. Neutral mononuclear [Au(C⋮CR)(NHEt 2 )] (R = SiMe 3, t Bu), [Au(C⋮CR)(PR‘ 3 )] (R = H, R‘ = Ph, C 6 H 4 OMe-4; R = CH 2 Cl, CH 2 Br, CH 2 OH, R‘ = Cy = cyclohexyl; R = SiMe 3, R‘ = Ph, C 6 H 4 OMe-4, Cy; R = t Bu, R‘ = Ph, Cy, C 6 H 4 OMe-4), [Au(C⋮CR)(CN t Bu)] (R = SiMe 3, t Bu), and [Au(C⋮CR){C(NH t Bu)(NEt 2 )}] (R = H, SiMe 3, t Bu) or dinuclear [(AuL) 2 {μ-C⋮C(CH 2 ) 5 C⋮C}] (L = PPh 3, CN t Bu, C(NH t Bu)(NEt 2 )) are obtained via a variety of synthetic methods: (i) reaction between [(PPh 3 ) 2 N][Au(C⋮CH) 2 ] and [Au(PR 3 ) 2 ]ClO 4, (ii) reaction of terminal alkynes with [Au(acac)(L)], (iii) reaction of [AuClL] complexes with terminal alkynes in diethylamine, (iv) substitution reactions ( e.g., [Au(C⋮CR)(NHEt 2 )] + PR‘ 3 ), (v) reaction of diethylamine with alkynyl isocyanide derivatives to give alkynylcarbene complexes. The crystal structures of [(PPh 3 ) 2 N][Au(C⋮CCH 2 OH) 2 ], [Au(C⋮CSiMe 3 )(CN t Bu)], and [Au(C⋮CR)(PR‘ 3 )] (R‘ = Cy, R = CH 2 Cl, CH 2 Br; R‘ = Ph, R = SiMe 3, t Bu) were determined.