Dithiolato complexes phosphines

One area of silver chemistry that has received much recent attention is the synthesis of multinuclear aggregates.315 Anionic metal dithiolato complexes such as K M(S2C202)2 were found to form adducts with silver(I) phosphines. In these complexes, the inert cations (K+) that accompanied the metallothio anions could be readily substituted by coordinatively unsaturated silver phosphines Ag(PR3)2. For dithiooxalto complexes this led to the isolation of a remarkable range of linkage isomers (34)-(37) 316,317... 

Phosphines also are able to (a) add to a vacant coordination site in planar dithiolenes or split dimers such as [Fe(mnt)2]2 to form52 square pyramidal adducts of structure (36) and (b) displace certain dithiolene ligands to form dithiolato complexes of the general structure (37). These reactions also are briefly discussed in Section 16.5.3.8. 

The period under discussion has seen intense interest in the recently discovered i7 -H2 complexes. The relevance of these to some isomerization reactions of square-planar complexes was reported in Volume 5 of this series, and is covered in another recent review. " More of these fluxional ds-dihydridoplatinum compounds have been reported, and the role of 17 -H2 derivatives in oxidative additions to d rhodium(I) and iridium(I) has been discussed. The increasing role of theoretical and bonding studies is reflected in four works relevant to 4-and 5-coordinate molecules. Electronic structure is related to chemical reactivity in the reactions of phosphine bases with d bis(l,l-dithiolato)platinum com-plexes. Huckel calculations on the reactions of bis(nitrogen donor) ligands with 16-electron platinum(II) complexes have been carried out, as has more work on symmetry selection rules for isomerization reactions, which includes pseudorotation of 5-coordinate complexes and square-planar to tetrahedral conversions of 4-coordinate molecules. ... 

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