Reaction of the iodo-bridged tungsten dimer [(PhN)W(CO) 2 I 2 ] 2 with 2 equiv of LiOCH 3 produced new dimers of the type [(PhN)W(CO) 2 I(OCH 3 )] 2 . The intermediate iodo-bridged dimer [(PhN)W(CO) 2 (μ-I)(OCH 3 )] 2 (5) reacted with PMe 3 , P(OMe) 3 or NH 2 C 6 H 2 Me 3 to yield mononuclear derivatives of the type (PhN)W(CO)I(OCH 3 )L 2 [for 10: L=PMe 3 , for 11: P(OMe) 3 ] or (PhN)W(CO) 2 I(OCH 3 )(NH 2 C 6 H 2 Me 3 ) (9). In solution, 5 slowly isomerized to [(PhN)W(CO) 2 I(μ-OCH 3 )] 2 (6), for which an X-ray crystal structure confirmed the presence of bridging methoxide ligands. Further reaction of 6 with excess LiOCH 3 resulted in substitution of methoxide for the remaining iodides of 6 to produce [(PhN)W(CO) 2 (OCH 3 ) 2 ] 2 (7) in low yield.