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The coordination chemistry of neutral thio-, seleno- and telluroether ligands towards the hard s-block, f-block and higher oxidation state early d-block metals has developed significantly over the 15 or so years. This has revealed several hitherto unknown classes of complexes and new insights into the chemistries of these hard-soft metal-ligand combinations.
NbCl4 reacts with the dithioethers MeS(CH2)nSMe (n = 2 or 3), iPrS(CH2)2SiPr or o-C6H4(CH2SEt)2 in a 1: 1 molar ratio in CH2Cl2 or toluene over several days, to give red or orange, paramagnetic complexes, [NbCl4(dithioether)]. Their X-ray crystal structures confirm distorted octahedral geometries with chelating dithioether. MeS(CH2)2SMe, alone, also forms an [NbCl4{MeS(CH2)2SMe}2] complex bsaed upon eight-coordinate Nb(IV) in a square antiprismatic geometry.
A new route to cationic complexes of Mg, Ca, Sr and Ba with 18-membered ring O S , O Se and O S donor macrocycles from metal acetonitrile complexes with weakly coordinating [BAr ] anions is described. The precursors used were [M(MeCN) ][BAr ] (M = Mg, x = 6; M = Ca, x = 8) and [M′(acacH)(MeCN) ][BAr ] (M′ = Sr or Ba).
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