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A new entry to low-valent, carbonyl-free tungsten phenylcarbyne complexes has been developed from W(CO) 6  via tungsten(II) alkyne complexes. The first step includes thermal decarbonylation of W(CO) 6  to fac-W(CO) 3 (MeCN) 3  and subsequent substitution of the acetonitrile ligands by EtNC or t-BuNC to give fac-W(CO) 3 (EtNC) 3  (1 a) or fac-W(CO) 3 (t-BuNC) 3  (1 b) in almost quantitative yields. Advantages of this indirect synthesis of 1 a and 1 b from W(CO) 6  are discussed in comparison to the previously described, CoCl 2  catalyzed transformation of W(CO) 6  with RNC to fac-W(CO) 3 (RNC) 3 . Compounds 1 a and 1 b are then quantitatively converted with Br 2  to W(CO) 2 (EtNC) 3 (Br) 2  (2 a) and W(CO) 2 (t-BuNC) 3 (Br) 2  (2b). 2 a and 2b react subsequently with PhC=CBr to give upon elimination of both CO ligands the carbonylfree compounds W(EtNC) 3 (η 2 -PhC=CBr)(Br) 2  (3a) and W(t-BuNC) 3 (η 2 -PhC=CBr)(Br) 2  (3b) in good yield. 3 a and 3b represent rare examples of complexes containing a 1-haloalkyne ligand. They are susceptible to nucleophilic attack at this ligand. Thus reaction of 3 a and 3 b with

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Basen-induzierte Alkin-Spaltung in W(II)-Komplexen – ein neuer Weg zu niedervalenten Carbin-Komplexen aus W(CO) 6  / Base-Induced Alkyne Cleavage in W(II) ComplexesaNew Way to Low Valent Carbyne Complexes from W(CO) 6