Binuclear diorganophosphinothioformamido complexes of gold(I): Synthesis and crystal structure of [Au(Ph2PC(S)NPh)]2 and related systems

Coordination modes of diphenylphosphinothioformamide in its neutral and deprotonated forms at gold(i)

“…The gold atoms in complex 3 exhibit linear geometry at the gold centres (C-Au-P angles of 175.9(2) and 176.4(2)Њ and C-Au-S angles of 175.1(2) and 174.8(2)Њ) with typical Au-C distances between 2.029(8) and 2.074(7) Å. The Au-P distances, of 2.273(2) and 2.270(2) Å, are slightly longer than in complex 1 (2.2254(7) Å) and compare well with those observed in [Au(Ph 2 PC(S)NPh)] 2 13 (2.265(5) and 2.271(5) Å), [Au(cHex 2 PC(S)NPh)] 2 13 (2.276(1) Å) or [Au(Ph 2 PCH 2 SPh)] 2 (CF 3 SO 3 ) 2 7 (2.2721(11) Å), while the Au-S distances in 3 (2.315(2) and 2.316(2) Å) are shorter (2.3619(11) Å) and closer to those found in [Au(Ph 2 PC-(S)NPh)] 2 13 (from 2.306(5) to 2.318(3) Å) or in [Au(cHex 2 PC-(S)NPh)] 2 13 (2.306(1) Å). Complex 3 also shows an N-H ؒ ؒ ؒ F hydrogen bond between adjacent tetranuclear units with an H ؒ ؒ ؒ F distance of 2.42 Å (Table 2).…”

“…The chemical shift of 50.7 ppm in the 31 P{ 1 H} NMR spectrum is similar to that obtained for the previously reported dimeric complex [Au{Ph 2 -PC(S)NMe}] 2 . 13 These facts seem to be in accordance with a process of simultaneous deprotonation of the aminic protons of two [Au(C 6 F 5 )(Ph 2 PC(S)N(H)Me)] units by the pentafluorophenyl rings of the adjacent units; whereby these act as Lewis bases producing pentafluorobenzene. An example of the deprotonating ability of the pentafluorophenyl group has previously been described 18 in the gold complex [Au(C 6 F 5 )PhP(O)H] and is in good agreement with our results.…”

“…Both independent dinuclear units of complex 3 also show intramolecular Au ؒ ؒ ؒ Au contacts of 3.0391(5) and 3.1631(5) Å, respectively. These distances are also longer than those in the related complexes [Au(Ph 2 PC(S)-NPh)] 2 13 (2.9241(1) and 2.919(1) Å), [Au(cHex 2 PC(S)NPh)] 2…”

“…2) crystallizes forming tetranuclear units formed by an intermolecular Au ؒ ؒ ؒ Au interaction of 3.2712(5) Å (Table 3) between two [Au 2 (C 6 F 5 ) 2 {PPh 2 -C(S)N(H)Me}] units; intermetallic distances between adjacent tetranuclear units are approximately 6 Å. This intermolecular Au ؒ ؒ ؒ Au interaction is longer than those found in the related complex [Au(Ph 2 PC(S)NPh)] 2 13 (3.146(1) Å) or in other dinuclear bridged gold() complexes that display inter-and intramolecular metal-metal interactions 24-27 (intermolecular Au ؒ ؒ ؒ Au distances between 2.954(1) 24 and 3.171(3) Å 26 ) and similar to that observed in the polymer [ClAu{Ph 2 P(CH 2 ) 8 -PPh 2 }AuCl] ∞ 28 (3.264(2) Å). Both independent dinuclear units of complex 3 also show intramolecular Au ؒ ؒ ؒ Au contacts of 3.0391(5) and 3.1631(5) Å, respectively.…”

“…In this paper we report the synthesis of new mono-and polynuclear gold() complexes with the ligand Ph 2 PC(S)N(H)Me and its corresponding anion [Ph 2 PC(S)NMe] Ϫ as a multi/ mixed-functional donor for gold(). Tiekink et al 12,13 have summarized the coordination capabilities of this type of ligands to different organometallic or metallic substrates, but a systematic study of the coordination capabilities of this ligand without varying metal centers has not been reported to date. In this paper we present two-or three-coordinated mononuclear complexes, dinuclear compounds, and also one tetranuclear complex formed via gold()-gold() intermolecular interactions.…”