Nickel(II), palladium(II), platinum(II), and platinum(IV) complexes of the dithiolate ligand, C5H4CS22-. Crystal structure and molecular geometry of bis(tetraethylammonium) bis(cyclopentadienedithiocarboxylato)nickelate(II)

Cyclopentadienylidene‐ and Fluoren‐9‐ylidene‐methane‐1,1‐dithiolato Metalates of Tin, Indium and Bismuth

“…Compared with the exocyclic C1−C2 bond (1.423(3) Å) of the protonated, uncoordinated ligand 2 , a shortening, thus a higher double bond character (1.384(2) Å) of this particular bond is observed. The C1−C2 bond length is comparable with the C1−C2 bond length in the only other structurally characterized complex [NEt 4 ][(CpCS 2 ) 2 Ni] (C1−C2 1.381(2) Å) [18] . Replacement of C−S−H in 1‐PPh 4 by C−S−In in 3‐NBu 4 does not have a significant influence on C1−S1, 2 1.7465(15) vs. 3 1.742(2) Å and only very little influence on non‐coordinated C1−S1 1.7485(14) Å).…”

“…Studies of the [CpCS 2 ] 2− ligand were mainly focusing on transition metal coordination with the exception of a tin(II) and tin(IV) complex [9] . The attention has centered on square‐planar, [15,18] less on tetrahedral, [15] octahedral [19] and disphenoidal d‐metal coordination compounds [9] . However, the characterization by XRD measurements is limited to a square‐planar coordinated Ni(II) complex [18] .…”

“…The attention has centered on square‐planar, [15,18] less on tetrahedral, [15] octahedral [19] and disphenoidal d‐metal coordination compounds [9] . However, the characterization by XRD measurements is limited to a square‐planar coordinated Ni(II) complex [18] . Electronic properties as well as the bonding situation were investigated by optical spectra coupled with electron spin resonance studies indicating a very covalent out‐of‐plane metal‐sulfur‐π‐bond [15] …”

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO2 or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

“…The coordination sphere can be considered as distorted square. In contrast to some known metal complexes with cyclopentadienedithiocarboxylate (C 5 H 4 CS 2 ) 2− ligand [58] , the C5‐C6 bond has to be described as single bond (1.45(1) Å) and with respect to the La−O bond lengths (La1−O1 2.507(6) Å, La1−OO2 2.562(5) Å) and ring C−C bond lengths (average 1.407 Å) in the molecular structure, it is plausible, that one electron of this dianion is delocalized over the CO 2 moiety while the other is allocated over the Cp backbone. The Cp backbone is only slightly out of the plain defined by the CO 2 moiety.…”

“…The importance of such O−H⋅⋅⋅O hydrogen bond activation of COX is reflected by the fact, that CS 2 is only inserted once, not twice into CH‐bonds of Cat[Cp] under similar conditions, plausibly a matter of weak or non‐existent S−H⋅⋅⋅S hydrogen bond interaction [54,58,59] …”