Dithiophosphonates

Few compounds with dithiophosphonate R(R 0)PS2 or dithiophosphinate R2PS2 ligands have been reported. The resulting complexes (347) and (348)911-913 also show a square planar coordination geometry. 

Fewer routes are known for the preparation of dithiophosphonic acids. Nevertheless sodium dithiophosphophonates have been prepared in high yields from reaction of dithiadiphosphetane disulfides with a sodium alkoxide or aryloxide in the corresponding alcohol solution (Equation 25).40,41... 

Phosphor-1,1-dithiolates comprise ligands derived from dithiophosphoric acid 0,0-dithioesters (further called simply dithiophosphates), dithiophosphinic acids (dithiophosphinates), and the hybrid dithiophosphonic acid O-monoes-ters (dithiophosphonates) (Scheme 1). 

The dithiophosphonic acid monoesters, RP(OR )(S)SH can be conveniently prepared by cleavage of dimeric, cyclic diphosphetane disulfides, [RP(S)S]2 with alcohols, silanols, or trialkylsilylalcohols180 and then can be converted into metal complexes M[SPR(OR )]2 without isolation.181 The substituted ferrocenyl anion, (N3C6H4CH20)(CpFeC5H4)PS2 has been prepared in two steps from P4Sio, ferrocene and hydroxymethylbenzotriazole (and its salt was used for the preparation of some nickel and rhodium complexes).182 Zwitter-ionic ferrocenylditiophosphonates,... 

Polymeric dithiophosphonate complexes of the type (80) have been prepared. The cobalt complex is tetrahedral and the nickel complex planar and both... 

Fackler and co-workers were able to correlate the relationship between the intermolecular Au- -Au interactions and the presence of photo-luminescence in a series of binuclear annular gold(I) dithiophosphonate complexes with different extents of intermolecular Au-Au interactions [58,59]. This not only enables one to predict the presence of any weak intermolecular Au- Au interactions based on the observed luminescence properties of this class of complexes, but also allows one to estimate the relative extent of such interactions. 

Die in ds. Handb., Bd. XII/1, S. 616 genannte Methode zur Synthese von Dithiophosphon-saure-anhydriden aus Phosphor(V)-sulfid und Aromaten laBt sich auch auf Thiophen iibertragen. Aus siedendem Thiophen, in dem Phosphor(V)-sulfid gelost ist, scheiden sich nach 48 Stdn. 86% Thiophen-2-dithiophosphonsdure-anhydrid kristallin ab662. 

Oxo-aIkansaure-nitrile und -amide reagieren mit 4-Methoxy-bcnzol-dithiophosphon-saure-anhydrid bei lstdgm. Erhitzen dcr Komponenten in Toluol auf 110°zu 2-(4-Me-thoxy-phenyl)-4-thioxo-3,4-dihydro-2H- l,3,2-oxazaphosphorin-2-sulfi-den (72-940/o)CMO ... 

L. Maier, Preparation, Structure and Properties of Thionophosphine Sulfides and Oxides (Dithiophosphonic and Monothiophosphonic Anhydrides), Topics in Phosphorus Chemistry 10, 129 (1980). 

An example of combining hnear synthons with tetrahedral synthons in the same ring is provided by the gold(I) complexes of dithiophosphonates and a mixed ring consisting of linear, angular, and tetrahedral synthons is illustrated by the gold(l) complex (Scheme 21). 

Efficient catalysts for direct episulfidation of alkenes by sulfur-atom donors are also diethyldithiocarbamate and dithiophosphonate molybdenum oxo complexes 302 and 303, respectively (Equation 43 Scheme 88 Table 13) <2003JA3871>. The most efficient sulfur-atom donor in this reaction is 2-phenylthiirane. The best results were obtained, in most cases, when 1 equiv of 2-phenylthiirane was used as sulfur-atom donor in deuterated benzene at 80 °C for 30 min. Reaction of /ra r-cyclooctene catalyzed by either of the oxomolybdenum complexes gave trans-epithiocyclooctane. When this reaction was carried out in the presence of 302, the yield of the corresponding thiirane was only 20%, whereas catalyst 303 converted the olefin in almost quantitative yield (Table 14). 

This section deals with a series of phosphor-1,1-dithiolates, which includes dithiophosphinates, M(S2PR2) , dithiophosphates, M[S2P(OR)2] , and dithiophosphonates, MIS R OR2)] Alternative names are phosphinodithioates, phosphorodithioates, and phosphonodithioates, respectively. The parent acids (proligands), (l)-(3) are shown in Scheme 1. ... 

Dithiophosphinic acids Dithiophosphoric acid 0,0-diesters Dithiophosphonic acid O-esters... 

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