Metal atoms carbon disulfide

Carbon disulfide forms complexes in which the metal has a low oxidation state with almost every transition metal. The complexes have been reviewed extensively.1 7,8 Three bonding modes are found end-on via S, if bonded and bridging between two metal atoms. The evidence for these three bonding types is largely spectroscopic and therefore limited. CS2 shows a variety of insertion and disproportionation reactions. 

The crystal structure of the carbon disulfide adduct of [(C6H5)3P] 3Pt has been solved (42). In this case, the Pt is bound to a carbon and one sulfur of the CS2 group. The Pt atom and its four directly-bound neighbors are coplanar, but the unbound sulfur is tipped out of this plane. Furthermore, the CS2 molecule is bent with a S-C-S angle of 136(4)°. It is an interesting question in this case as to the oxidation state of the metal relative to the geometry of the complex. 

The infrared spectra of a number of hydroxyalkylmetallocenes have been interpreted in terms of hydrogen bonding involving the metal atom. The best example is provided by the epimeric alcohols (XVI and XVII), which exhibit absorption at 3610 and 3561 cm. , respectively, in dilute carbon disulfide solution 23, 24, 59), The low frequency band which, with the absorption near 3600 cm. appears as well in the spectra of acyclic a- and jS-hydroxyalkylferrocenes, has been assigned to the metal-bound hydrogen bond 23, 24, 59, 61),... 

X-Ray structural determination has revealed the existence of two classes of compounds with a carbon disulfide bridge between two metals. In the first class one metal is bonded to CS2 (Table 1). The second class can be described as metallodithiocarboxylato complexes in which the ligand has a metal bonded to the carbon atom of the CS2 group (Table 2). In general the transition metal groups are less effective in the stabilization of an E—CS2 bond than the first-row main-group donor atoms. Dithiocarbene complexes of the type (18) were also synthesized and a crystal structure confirmed the bonding mode. ... 

Copper complexes of bis(2,2 -dipyridyl)dithiocarbamate have been prepared upon insertion of carbon disulfide into the copper-nitrogen bonds of the corresponding 2,2 -dipyridylamine (dpa) complexes (195, 196). Kumar and Tuck (195) initially noted this behavior for [Cu(dpa)] , [Cu(dpa)2], and [Cu(dpa)(dppe)l [dppe = l,2-bis(diphenylphosphino)ethane], but characterization was made only on the basis of the presence of characteristic v(C—S) and v(C—N) bands in their IR spectra. Later, this was confirmed by the X-ray crystal structure of [Cu(S2Cdpa)2], formed upon slow evaporation of a carbon disulfide solution of [Cu(dpa)2] (Eq. 21) (196). The transformation is actually quite complex as in the dpa complex, metal coordination is through the nitrogen atoms of the pyridyl rings (197), and thus a rearrangement to the amide form must occur prior to carbon disulfide insertion. 

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