Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-κ3S,S′,P}2] and [W{P(2-SC6H4)3-κ4S,S′,S″,P}2]: Synthesis, structures and redox chemistry

Abstract

PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

Reaction of a heterotopic P,SAs ligand with group 10 metal(ii) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt

“…The phosphorus and arsenic atoms are in a slightly distorted trigonalpyramidal environment (Table 1). The C-E-C bond angles are similar to those found in phosphanylarylthiols, 9 o-(diphenylphosphanyl)thioanisole 10 and thioacylsulfanylarsines. 11 The P-C bond lengths are in the expected range.…”

Heteropolytopic phosphanylarylthiolato ligands: formation of cis isomers of nickel(ii), palladium(ii) and platinum(ii) complexes with 1-P(Biph)-2-SHC6H4 (Biph = 1,1′-biphenyl-2,2′-diyl)

“…Yield: 2.26 g, 10.3 mmol (83% based on 2,2′-dilithiobiphenyl). Data for 5-N,N-diisopropylamino-dibenzo [b,d]phosphole: 1 H NMR (δ, CDCl 3 ): 7.83 (d, 3 J HH = 8 Hz, 2H, aryl-H-1,9), 7.68 (t, 2H, aryl-H-4,6), 7.39 (t, 2H, aryl-H-2,8), 7.29 (m, 2H, aryl-H-3,7), 3.31 (br s, 1H, CH), 2.60 (br s, 1H, CH), 1.43 (br s, 6H, CH 3 ), 0.85 (br s, 6H, CH 3 ). 31 P{ 1 H} NMR (δ, CDCl 3 ): 31.6.…”

“…1,2 Among the most prominent phosphanylarylthiolate ligands are 1-PPh 2 -2-SHC 6 H 4 (PSH), PhP(2-SHC 6 H 4 ) 2 (PS 2 H 2 ) and P(2-SHC 6 H 4 ) 3 (PS 3 H 3 ), and their coordination chemistry is well established. 1,3,4 The P,S ligands were synthesised by the reaction of lithium 2-lithiobenzenethiolate, 1-Li-2-SLi-C 6 H 4 , with chlorophosphines PCl n Ph 3−n (n = 1-3). 5,6 Most of the known complexes of nickel, palladium and platinum with phenylene-bridged phosphanylthiolato ligands have been prepared by dealkylation of the corresponding thioether complexes.…”

Stabilisation of an inorganic digallane by the phosphinobisthiolato P,S,S pincer ligand PPh(2-SC6H4)2

“…A few colourless crystals suitable for X-ray diffraction were obtained from a concentrated solution of 2 in diglyme at room temperature in 3 days. 1 H NMR (d,CDCl 3 ,20H,phenyl),26H,aryl). 31 P{ 1 H} NMR (d, CDCl 3 , ppm): 22.9 (PPh 4 ), À23.9, À29.3 (br).…”

“…Of these, phosphinothiolates derived from thiophenol [PPh 2 H 4 ) (PSH), PPh(2-HSC 6 H 4 ) 2 (PS 2 H 2 ) and P(2-HSC 6 H 4 ) 3 (PS 3 H 3 )] have been shown to be highly versatile ligands that form stable complexes with a wide range of elements, especially compounds of the heavier transition metals. 1,2 In particular, the PS 2 H 2 ligand is interesting due to the wide range of potential coordination patterns which result from combinations of phosphorus and sulfur coordination: as P,S,S pincer ligands, as bidentate P,S or S,S ligands, as monodentate S or P ligands, and, additionally, as doubly or triply bridging ligands. Although the chemistry of the PS 2 H 2 ligand with transition metals has been studied to some extent, 1a,2 only a few complexes of main group metals have been reported so far.…”