Mono‐ and Dimetallic Cyano Complexes with {Mo(η³‐allyl)(CO)₂(N−N)} Fragments

Treatment of [MoCl(η 3 ‐allyl)(CO) 2 (phen)] with NaCN in CH 2 Cl 2 /MeOH afforded [Mo(CN)(η 3 ‐allyl)(CO) 2 (phen)] [allyl = C 3 H 5 ( 1a ); 2‐MeC 3 H 4 ( 1b )] as the sole products (no products of cyanide attack on the allyl group were detected). Treatment of 1a , b with [Mo(OTf)(η 3 ‐C 3 H 5 )(CO) 2 (phen)] and NaBAr′ 4 in CH 2 Cl 2 yielded the compounds [{Mo(η 3 allyl)(CO) 2 (phen)}(μ‐CN){Mo(η 3 ‐C 3 H 5 )(CO) 2 (phen)}]BAr′ 4 ( 2a , b ). Analogous treatment of 1a with fac ‐[M(OTf)(CO) 3 (bipy)] (M = Mn, Re) and NaBAr′ 4 resulted in the synthesis of [{Mo(η 3 ‐C 3 H 5 )(CO) 2 (phen)}(μ‐CN){M(CO) 3 (bipy)}]BAr′ 4 ( 3 , 4 ), in which the C and N atoms of the cyano bridge are bonded to Mo and M (M = Mn, Re), respectively. The linkage isomer of 4 (C and N atoms of the cyano group bonded to Re and Mo, respectively) ( 6 ) was prepared by treatment of [Re(CN)(CO) 3 (bipy)] ( 5 ) with [Mo(OTf)(η 3 ‐C 3 H 5 )(CO) 2 (phen)] and NaBAr′ 4 . Compounds 1a , 2b , 3 , and 6 were characterized by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)