Donor bidentate sulfur

Fig, 1 provides a listing of the various sulfur donor ligands whose complexes have been the subject of considerable research. The list of ligands in Fig. 1 is not exhaustive since only potentially bidentate ligands are given. The electronic properties of complexes with bidentate sulfur donor ligands are usually similar although their physical properties, e.g., solubility, can vary widely. This review deals primarily with dithio- and diselenophosphate complexes however, related complexes are discussed wherever they are pertinent to the present discussion. 

Published data on the volatility of complexes of the transition metals including chromium with bidentate sulfur and sulfur-oxygen donor ligands have been summarized.1042... 

Other complexes of bidentate sulfur donor ligands "SCHjCHjS"... 

Detailed structural parameters are given in Table 13. On the other hand, the bidentate sulfur donor ligands in [Te (SPPh2)2N 2] form six-membered chelate rings with large normalized bites, b - 1.37, and the complex has an undistorted planar rectangular structure, 4>a = 47.0°, [Pg.60]

Many of the general characteristics of dithiolene ligands and their metal complexes described in other chapters of this volume are also useful to Nature. A recurring theme of dithiolene coordination chemistry is their ability to stabilize multiple redox states for a wide variety of metals. The access to multiple redox states combined with a propensity for substantial electronic delocalization likely influenced Nature s choice of dithiolene as a chelating ligand over other potential bidentate sulfur donors. 

A dinuclear selenide complex anion [Au2(M-Se)2(Se4)2] is the product of the reaction" between [AuCN] and Na2 Ses. Square-planar gold(IIl) complexes are readily formed by a variety of bidentate sulfur-donor ligands such as toluene-1,2-dithiolate, maleonitriledithiolate, and dithiocarbamate. On oxidation with CI2 or Br2, [ Au(S2CNR)2 2] forms Au -Au complexes, which may be oxidized further to an Au complex. 

The first molecular, 6-coordinate complexes which proved to adopt a nonoctahedral structure contain the bidentate, sulfur-donor ligands of the general structures, I and II ... 

Recent Advances in the Chemistry of Transition Metal Complexes of Unsaturated Bidentate Sulfur Donor Ligands (Metal Dithienes)... 

Much of the interest in the bidentate sulfur donor ligands was the discovery that trigonal prismatic as well as octahedral coordination could occur. Thus, X-ray studies of Re(S2C2Ph2)3 and V(S2C2Ph2)3 showed trigonal prismatic geometry. However, Gray and co-workers have concluded from electronic spectral measurements that Ti(nrnt) (mnt = maleonitriledithiolate) has a severely distorted octahedral structure. 

Diphenyl-2-thienylphosphine is expected to serve as a bidentate ligand by coordination of either the phosphorus and sulfur atoms or the phosphorus atom and TT-electrons of the heteroring. Reaction of this phosphine with [Rc2(CO)lo] yields the species where both the sulfur and phosphorus atoms serve as the donor sites (960M786). 

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