Abstract

Upon oxidative decarbonylation with iodine, trans-I(CO) 2L 2WCNEt 2 complexes (L 2 = 2,2′-bipyridyl (2,2′-bipy); 1,10-phenanthroline (ophen)) (I, II) are quantitatively transformed to the seven-coordinated, carbonyl-containing carbyne complexes (I) 3(CO)L 2WCNEt 2 (L 2 = 2,2′-bipy, ophen) (III, IV) with tungsten in a high oxidation state. Complexes III and IV react with excess PMe 3 with reductive elimination of PMe 3I +I − to yield the cationic carbyne complexes [(PMe 3) 2(CO)-L 2WCNEt 2] +I − (V, VI).

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