Abstract
Summary The butadiyne complexes [W 2 Cl 8 (Me 3 SiC≡CC≡CSiMe 3 )] x and [W 2 Cl 8 (IC≡CC≡CI)] x are synthesized by the reaction of tungsten hexachloride with Me 3 SiC≡CC≡SiMe 3 and IC≡CC≡CI, respectively, in boiling CCl 4 . The complexes are associated by chloro bridges WCl 2 W. They react with pyridine or diethyl ether to form the adducts [W 2 Cl 8 (XC≡CC≡CX)Y 2 ] (X = SiMe 3 , I; Y = pyridine, diethyl ether). The thermally and mechanically very stable diiodobutadiyne complex reacts with (PPh 3 CH 2 I)Cl forming the chloro complex (PPh 3 CH 2 I) 2 [W 2 Cl 10 (IC≡CC≡CI)] which is very soluble in dichloromethane. This chloro complex reacts with silver chloride to form the dichlorobutadiyne complex (PPh 3 CH 2 I) 2 [W 2 Cl 10 (ClC≡CC≡CCl)] which is also very stable. The results of IR and 13 C NMR spectra correspond to the carbon-carbon triple bonds acting as four-electron donors, and the bonding to tungsten is best described as being of the metallacyclopropene type.
Published Version
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