Luminescent Phosphine Gold(I) Thiolates:  Correlation between Crystal Structure and Photoluminescent Properties in [R₃PAu{SC(OMe)NC₆H₄NO₂-4}] (R = Et, Cy, Ph) and [(Ph₂P-R-PPh₂){AuSC(OMe)NC₆H₄NO₂-4}₂] (R = CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, Fc)

Abstract

X-ray crystallography shows the gold atoms in [R3PAu{SC(OMe)=NC6H4NO2-4}] (R = Et, Cy, Ph; 1-3, respectively) and [(Ph2P-R-PPh2){AuSC(OMe)=NC6H4NO2-4}(2)] (R = CH2, (CH2)2, (CH2)3, (CH2)4, Fc; 4-8, respectively) are linearly coordinated by phosphorus and thiolate-sulfur; weak intramolecular Au...O interactions are featured in all structures. The smaller ethyl substituents in 1 allow for supramolecular association via Au...S and Au...Au interactions that are not found in 2 and 3, which contain larger phosphorus-bound Cy and Ph groups, respectively. Intramolecular Au...Au interactions are found in the dppm, dppe, dppp, and Fc structures but not in the dppp analogue, for which an anti conformation was found. The structures have been correlated with the results from photophysical study conducted in the solid state. Thus, photoexcitation of 1-7 with lambda > 350 in the solid state and in solution produces green and blue luminescence, respectively. The spectra in each medium are remarkably similar to each other, and so the emission energy and excitation maxima observed for 1-7 appear to be independent of the nature of the ancillary phosphines, as well as the presence or absence of Au...Au interactions, either intermolecularly or intramolecularly.

Synthesis, structures and in vitro cytotoxicity of some platinum(II) complexes containing thiocarbamate esters

“…92.20(11)°and 87.80(11)°, deviate only very slightly from the 90°e xpected for square planar geometry. Small deviations from the ideal geometry may be traced to the presence of a close intramolecular PÁ Á ÁO1 separation = 3.036(9) Å; such metalÁ Á ÁO interactions are often seen in the structural chemistry of these ligands [8][9][10]. The Pt-P bond length of 2.272(3) Å in 4 is similar to those observed in other PTA metal complexes and in the same way, the Pt-S distance of 2.345(3) Å is similar to that found in other complexes containing S-coordinated aryl thiocarbamate esters.…”

“…The palladium complex [Pd{jN,S-PhN@C(S)OMe}{jS-PhN@C(S)OMe}(PPh 3 )] is the only example in which both coordination modes (anionic S À ligand and N,S-chelate ligand) are present in the same molecule [7]. To the best of our knowledge, the only known complexes of this type that have been prepared by direct reaction of the neutral thiocarbamate esters with transition metal chloride precursors in the presence of base are the above mentioned Pd chelates as well as the mono-and dinuclear gold(I) phosphine complexes [Au{ArN@C(S)OMe}(P)] and [Au 2 {ArN@C(S)OMe} 2 (l-PP)] (P and PP = mono-and bidentate phosphine ligands, respectively) reported by Tiekink [8][9][10]. Ever since the accidental discovery of the cytotoxic properties of cis-[PtCl 2 (NH 3 ) 2 ] by Rosenberg almost 40 years ago [11], cytotoxicity studies of many platinum compounds have been carried out [12].…”

Gold–Gold Interactions

“…Other examples of complexes [Au 2 X 2 (P$P)] that show similar structures to those in Figure 2.38a include anionic X ligands such as thiolates [211][212][213] or triphenylsilyl [214], with P$P ¼ dppm; X ¼ RC:C (R ¼ Ph, 4-OMe-C 6 H 4 ) with P$P ¼ N,N-bis (diphenylphosphino)propylamine [215]; X ¼ SC(OMe) ¼ NC 6 H 4 -4-(NO 2 ) with P$P ¼ (PPh 2 ) 2 (CH 2 ) n (n ¼ 1-4, no aurophilic interactions are found for n ¼ 4) or dppf [216]; X ¼ [S 2 P(R)(OR)] (R ¼ p-C 6 H 4 -OCH 3 ; R ¼ c-C 5 H 9 ), with P$P ¼ (PPh 2 ) 2 (CH 2 ) n [n ¼ 1-4; only for n ¼ 1 intramolecular interactions are present, for the other three Other derivatives with thiolates as anionic ligands which display chain structures are [Au 2 (SR) 2 (P$P)] (R ¼ Ph, P$P ¼ 1,2-bis(diphenylphosphino)ethene; R ¼ S-p-4-Me-C 6 H 4 , P$P ¼ PPh 2 (CH 2 ) 5 PPh 2 ) and [Au 2 Cl(SPh)(P$P)] (P$P ¼ 1,2-bis(diphenylphosphino)ethene) [26,[218][219][220]. In complexes [Au 2 {SC 6 H 4 -2-(C(¼O) Y)} 2 (m-dppf)], when Y ¼ NHMe intermolecular interactions lead to the formation of chains (Figure 2.40c).…”

Synthesis and structures of gold(I) phosphine complexes containing monoanionic selenocarbamate ester ligands

“…However, to date no complexes containing deprotonated, monoanionic N-aryl-O-akylselenocarbamate ligands are known. Given that gold(I) phosphine complexes containing ArNHC(S)OMe (Ar = Ph, 4-NO 2 C 6 H 4 ) form a variety of supramolecular structures and are also strongly luminescent [16][17][18][19], we were interested in exploring the so far unknown chemistry of their selenium counterparts, in particular focusing on N-phenyl-O-methylselenocarbamate. The results of this investigation are presented herein [20].…”