UEBERGANGSMETALL-FULVEN-KOMPLEXE. XXVIII. REAKTIONEN VON (FULVEN)Cr(CO)3-KOMPLEXEN UND Α-FERROCENYL-CARBENIUMIONEN MIT NUKLEOPHILEN

Article abstract of DOI:10.1016/0022-328X(86)80197-8

Tricarbonyl(fulvene)chromium complexes react with anionic nucleophiles to give functionally substituted cyclopentadienyl derivatives.The nucleophilic attack occurs at the exocyclic carbon atom of the fulvene ligand.Addition of PPh2^- to (η⁶-6,6-dimethylfulvene)Cr(CO)3 (1) yields the novel anion <(η⁵-C5H4C(CH3)2PPh2)Cr(CO)3>^-, which can be isolated as a K⁺, (C2H5)4N⁺, (C6H5)4P⁺, or Tl⁺ derivative (2-5).The potassium salt of the uncoordinated C5H4C(CH3)2PPh2^- anion (7) is obtained by treatment of 6,6-dimethylfulvene with KPPh2*2C4H8O2.Similarly, NaC5H5 reacts with 1 to give Na<η⁵-C5H4C(CH3)2C5H5)Cr(CO)3> (8).The reactions of (6-dimethylaminofulvene)Cr(CO)3 (15) with nucleophiles are accompanied by elimination of dimethylamine.Addition of Ph3P=CH2 to 15 gives an unstable product, but after reaction of 6-dimethylaminofulvene with Ph3P=CH2, the free ligand C5H4=CHCH=PPh3 (17) can be isolated in moderate yields.Deeply colored anions of the type <(η⁵:η⁵-C5H4C(R)=C5H4)Cr2(CO)6>^- (R = H, N(CH3)2 are synthesized by reaction of 15 or (6-dimethylamino-6-methylthiofulvene)Cr(CO)3 with NaC5H5 and subsequent complexation of the mononuclear intermediate with (CH3CN)3Cr(CO)3.In addition, the synthesis of the new fulvene complexes M(CO)3 (23,24; M = Cr, Mo) is described.The investigation is extended to α-ferrocenylcarbenium ions, which are isoelectronic with (fulvene)Cr(CO)3 complexes. <(η⁵-C5H5)Fe(C5H4CPh2)>⁺ BF4^- (25) adds tertiary phosphines at the exocyclic carbon atom to give phosphonium salts of the type <(η⁵-C5H4)Fe(C5H4CPh2PR3)>⁺ BF4^-.A CO-substitution product of a tricarbonyl(fulvene)chromium complex is obtained for the first time by irradiation of (η⁶-6,6-diphenylfulvene)Cr(CO)3 in the presence of PPh3.In addition, an improved synthesis of the (CH3CN)3M(CO)3 complexes (M = Cr, Mo, W) is reported.