ISSN:
1572-8854
Source:
Springer Online Journal Archives 1860-2000
Topics:
Geosciences
,
Physics
Notes:
Abstract The reactions in THF or benzene between Cp2 M (HgX)2 ·x HgX 2 (M = Mo or W; O ⩽x ⩽ 1;X − = Cl−, Br−, I−, SCN−, OAc−) and sodium diethyl-dithiocarbamate $$\begin{gathered} Cp_2 M\left( {HgX} \right)_2 .xHgX_2 + \left( {2 + x} \right)Nadtc \rightleftharpoons Cp_2 M\left( {Hgdtc} \right)_2 \hfill \\ + xHg\left( {dtc} \right)_2 + \left( {2 + x} \right)NaX \hfill \\ \end{gathered} $$ as well as between Cp2 MH2 and mercury diethyldithiocarbamate $$x2Cp_2 MH_2 + 2Hg\left( {dtc} \right)_{2 - } Cp_2 M\left( {Hgdtc} \right)_2 + \left\{ {Cp_2 Mdtc} \right\}dtc + 2H_2 $$ give the compound Cp2 M(Hgdtc)2 (dtc is diethyldithiocarbamate anion). The structure of the molybdenum complex determined by the X-ray method (a = 12.776(4),b = 7.835(4),c = 27.397(7) Å β = 111.18(2) °; space groupC2/c (No. 15);Z = 4) consists of discrete molecules occupying special positions on two-fold axes. A short Mo-Hg distance of 2.643(8) Å and a rather long Hg-S one of 2.50(2) Å were found. The diethyldithiocarbamate anion behaves like a monodentate ligand. IR and1H,13C NMR results agree with the molecular structure determination and confirm a weak bond between mercury and dithiocarbamate and strong molybdenum-mercury bond. A considerable solvent effect (C6D6 vs. CDCl3 solutions) has been observed on the1H chemical shifts of both dtc and Cp ligands. The {Cp2Modtc}+ X − (X = dtc and PF6) complexes, although not obtained in a pure form, were included in the discussion of the spectroscopic features of those with theM-Hg bonds.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01645348
Permalink