Synthese, Struktur und Charakterisierung von Titan-, Zink-, Nickel- und Palladium-Thioether-Thiolat-Komplexen heterocyclischer 1,2-Dithiolate

Abstract

Synthese und Eigenschaften von Gemischtligandenkomplexen der Thioether‐Thiolat‐Liganden 4‐Methylthio‐1,3‐dithiol‐2‐on‐5‐thiolat (dmidCH3), 4‐Methylthio‐1,3‐dithiol‐2‐thion‐5‐thiolat (dmitCH3) und 4‐Methylthio‐1,3‐dithiol‐2‐selon‐5‐thiolat (dmiseCH3) werden beschrieben. Die Röntgenkristallstrukturanalysen von Cp ′2Ti(dmidCH3)2 (Cp′ = Methylcyclopentadienyl), von zwei polymorphen Modifikationen des (tmeda)Zn(dmitCH3)2 [tmeda = 1,2‐Bis(dimethylamino)ethan] sowie von (dppe)Ni(dmitCH3)2 und (dppe)Pd(dmitCH3)2 [dppe = 1,2‐Bis(diphenylphosphino)ethan] werden vorgestellt.

Platinum(II) Complexes Bearing a Thiolate/Thioether Ligand – Hemilability vs. Dealkylation

“…The apical Pt ··· S distance of 8 approaches the values reported in platinum(II)–1,4,7‐trithiacyclononane complexes (2.84–2.97 Å) 24. The molecular structure of 8 compares well with that reported for the analogous compound cis ‐[Pd(η 2 ‐dppe) L 2 ], in which a close Pd ··· S(thiomethyl) contact of 3.11 Å was pointed out 4b. The intermolecular interactions observed in the solid‐state packing diagram of 8 along the bc plane are worth mentioning; the S ··· S contacts of 3.416 Å (S4 ··· S8) and 3.421 Å (S3 ··· S3) fall below the sum of the Van der Waals radii of two S atoms (3.70 Å) and give rise to a 2D supramolecular network (see Supporting Information).…”

“…As mentioned in the introduction, such a combination of η 1 ‐ and η 2 ‐ L ligands has already been observed in [Ni(dppe) L 2 ]. However, in this case, the difference in strength of the interactions between the metal centre and the two types of sulfur atoms is much more pronounced 4b. Compared to the value measured in centrosymmetric 1 , the Pt–P bond in 3 , trans to Pt–S thioether , is significantly stronger [2.2593(11) vs. 2.3339(5) Å].…”

“…31 P{ 1 H} NMR spectra were recorded at 300.13 MHz with a Bruker DRX 300 spectrometer. Cs L ,4b cis ‐[Pt(PEt 3 ) 2 Cl 2 ],25 cis ‐[Pt(PPh 3 ) 2 Cl 2 ],26 [Pt(dppm)Cl 2 ]27 and [Pt(dppe)Cl 2 ]28 were prepared according to literature procedures.…”

“…The parent dithiolene ligand, 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate (dmit 2– ), is one of the most studied dithiolene ligands and has applications in conducting materials 7. The coordinating ability and structural aspects of L have been studied by Olk et al with several other transition metals 4a,4b. Its coordination mode has been identified as monodentate through the thiolate sulfur atom in (Ph 3 P) 3 Ag L , (Ph 3 P) 2 Au L , Cp 2 Ti L 2 , (tmeda)Zn L 2 [tmeda = 1,2‐bis(dimethylamino)ethane] and (dppe)Pd L 2 [dppe = 1,2‐bis(diphenylphosphanyl)ethane], whereas the mixed thiolate/thioether ligand acts as a bidentate ligand in (Ph 3 P) 2 Cu L .…”

μ-Oxo-bis[trichlorobis(dimethylsulfane)titanium(IV)]

“…The quality of these ®lms was found to be as high as those obtained from the corresponding two-component processes. Along with the CVD studies, the properties of thio and seleno ethers have been investigated (Levason et al, 2000;Wilson et al, 2003;Zeltner et al, 1999). The X-ray structure determination of [(Me 2 S) 2 Cl 3 Ti] 2 ("-O), (I), is reported here.…”