Gold(I) Complexes of Phosphaalkynes

Abstract

Cationic gold(I) complexes of phosphaalkynes are formed by the interaction of [PtBu 2 (o-biphenyl)AuCl] with AgSbF 6 and an excess amount of RCϵP in CH 2 Cl 2 at room temperature. Free and coordinated phosphaalkyne readily exchange [a]

Homoleptic Phosphaalkyne Complexes of Silver(I)

“…In 1 , the perpendicular from Ag onto the C≡P bond cuts the bond at 0.52 Å ( d (PC)=1.549(11) Å) and in 2 at 0.53 Å ( d (PC)=1.58(2) Å). A similar behavior has recently been found for heteroleptic Au + complexes of different phosphaalkynes …”

(CF3)3Au as a Highly Acidic Organogold(III) Fragment

“…Although sought by different approaches, no minimum was found for side‐on coordination in the latter case. Side‐on coordination of the phosphaalkyne ligand was experimentally found in the cationic gold(I) complex [(R t Bu 2 P)Au(η 2 ‐P≡C t Bu)][SbF 6 ] (R=C 6 H 4 Ph‐2) …”

“…The lower stability of (CF 3 ) 3 Au(PC 5 H 5 )i nc omparison with (CF 3 ) 3 Au(NC 5 H 5 )c an be attributed to the phosphabenzene ligand being aw eaker s donor and better p acceptort han py. [67] Identical stabilization is attained with the prototypical p-acceptor ligandsC Oa nd PF 3 : D e = 90 kJ mol À1 .T heir complexes are the least stable in the whole set under study.A si nt he case of phosphabenzene, the poor s-donora bility of the CO and PF 3 ligands results in weaker [Au]ÀL s bonds. These Lewis bases are well known as typical weakly coordinating ligands.…”

Organophosphorus Compounds in Organic Electronics

“…Russell and co‐workers reported, in a VT‐NMR study, the first cationic phosphine‐supported phosphaalkyne–Au complex showing a dynamic situation of free and coordinated P centers through an associative mechanism. The η 2 ‐coordination of the C≡P to the cationic [Au(PR 3 )] + system ( 68 ; Figure ) gives an almost unaltered C≡P distance 1.569(12) Å, compared to uncoordinated phosphaalkynes preserving their triple bond character . The same group has demonstrated end‐on coordination of trimethylsilylphosphaalkyne to Mo ( 69 ; Figure ) and the potential desilylation to produce a cyaphide (C≡P − ) ligand, that is, the phosphorus analogue of cyanide.…”

“…The h 2 -coordination of the CPt ot he cationic [Au(PR 3 )] + system (68; Figure 13) gives an almost unaltered CPd istance 1.569(12) , compared to uncoordinatedp hosphaalkynes preserving their triple bond character. [117] The same group has demonstrated end-on coordination of trimethylsilylphosphaalkyne to Mo (69; Figure 13) and the potentiald esilylationt op roduce ac yaphide (CP À )l igand,t hat is, the phosphorus analogue of cyanide. This partial desilylation presumably gives the cyaphide-trimethylsilylphosphaalkynec omplex [Mo{Me 3 SiCP)(C P)(dppe) 2 }] À [118] as an interesting buildingb lock for the construction of cyaphide-bridged (M-PC-M')l inear inorganic oligoand polymers.…”