Reaction and subsequent transformation of anionic acetylide–carbene complexes using the Ph3PAu+ fragment

Abstract

The metallated Fischer-type carbene complexes (CO)(5)M=C(NMe(2))C[triple bond]CLi (M = Cr, W) react with Ph(3)PAuNO(3) to form the beta-substituted products (CO)(5)M=C(NMe(2))C[triple bond]CAuPPh(3). In solution these products isomerise by formal metal fragment exchange to furnish Ph(3)PAuC(=NMe(2))C[triple bond]CM(CO)(5). A preliminary kinetic investigation by means of (1)H-NMR spectroscopy indicates an unusual and complicated reaction mechanism. Model DFT calculations predict small energy differences between the products before and after the metal fragment exchange.

Lithiation of diynyl–ruthenium complexes: Routes to novel metallated functional diynes

“…We have previously described the synthesis of {Au(C^CC^CH)} 2 (m-dppm) from (AuCl) 2 (m-dppm) and HC^CC^CH under Cadiot-Chodkiewicz conditions, while the tetrametallic derivative {Cp(OC) 3 WC^CC^CAu} 2 (m-dppm) was similarly formed from W(C^CC^CH)(CO) 3 Cp and (AuCl) 2 (mdppm) [27]. The related ruthenium complex {Cp*(dppe) RuC^CC^CAu} 2 (m-dppm) 17 could not be prepared in this manner.…”

“…Orange LiC^CC^CW(CO) 3 Cp reacts with SiClMe 3 and MnCl(CO) 5 to give the silylated and manganated diynyl complexes, respectively [17]. The reaction between Li 2 C 4 (thf) n and fac-W(CO) 3 [20]. Lithio derivatives of Fe(C^CC^CH)(CO)(L)Cp (L ¼ CO, PPh 3 ) react with SiClMe 3 and MX(CO) 3 Cp (M ¼ Mo, W) [21].…”

“…Deprotonation of W(C^CC^CH)(CO) 3 Cp is achieved with bulky LDA, smaller LiR reagents attacking the CO groups. Orange LiC^CC^CW(CO) 3 Cp reacts with SiClMe 3 and MnCl(CO) 5 to give the silylated and manganated diynyl complexes, respectively [17]. The reaction between Li 2 C 4 (thf) n and fac-W(CO) 3 [20].…”

“…and L n M {C^CC(NMe 2 )]M(CO) 5 } [L n M ¼ trans-FeCl(dmpe) 2 , transPdCl(PEt 3 ) 2 , trans-PdCl(C^CH)(PEt 3 ) 2 , Au(PPh 3 ), to give monosubstituted products; TiCl 2 Cp 2 , trans-FeCl 2 (dmpe) 2 , MCl 2 (PEt 3 ) 2 (M ¼ Ni, Pd, Pt), HgCl 2 , to give disubstituted complexes] [2,3]. Isomerisation of the Au(PPh 3 ) derivative to (Ph 3 P) AuC(NMe 2 )]C]C]M(CO) 5 occurs upon standing in solution [3].…”

“…and L n M {C^CC(NMe 2 )]M(CO) 5 } [L n M ¼ trans-FeCl(dmpe) 2 , transPdCl(PEt 3 ) 2 , trans-PdCl(C^CH)(PEt 3 ) 2 , Au(PPh 3 ), to give monosubstituted products; TiCl 2 Cp 2 , trans-FeCl 2 (dmpe) 2 , MCl 2 (PEt 3 ) 2 (M ¼ Ni, Pd, Pt), HgCl 2 , to give disubstituted complexes] [2,3]. Isomerisation of the Au(PPh 3 ) derivative to (Ph 3 P) AuC(NMe 2 )]C]C]M(CO) 5 occurs upon standing in solution [3]. Extension of the carbon chain was achieved by reaction of the ethynylcarbene with LiBu/I 2 to give IC^CC(NMe 2 )] M(CO) 5 , followed by Cu(I)-catalysed coupling with IC^CeC^CSiMe to give (OC) 5 W]C(NMe 2 )(C^C) 3 SiMe 3 , desilylation and reaction with LiBu/HgCl 2 to give Hg {(C^C) 3 C(NMe 2 )]W(CO) 5 } 2 .…”