TY - JOUR

T1 - Übergangsmetall-fulven-komplexe. XXVIII. Reaktionen von (fulven)Cr(CO)3-komplexen und α-ferrocenyl-carbeniumionen mit nukleophilen

AU - Edelmann, Frank

AU - Behrens, Peter

AU - Behrens, Sabine

AU - Behrens, Ulrich

PY - 1986/8/26

Y1 - 1986/8/26

N2 - 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 Ph3PCH2 to 15 gives an unstable product, but after reaction of 6-dimethylaminofulvene with Ph3PCH2, the free ligand C5H4CHCHPPh3 (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 [C5H4CH(CHCH)2N(CH3)Ph]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-C5H5)Fe(C5H4CPh2PR3)]+BF4-. A CO-substititution 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.

AB - 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 Ph3PCH2 to 15 gives an unstable product, but after reaction of 6-dimethylaminofulvene with Ph3PCH2, the free ligand C5H4CHCHPPh3 (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 [C5H4CH(CHCH)2N(CH3)Ph]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-C5H5)Fe(C5H4CPh2PR3)]+BF4-. A CO-substititution 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.

UR - http://www.scopus.com/inward/record.url?scp=0040047026&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(86)80197-8

DO - 10.1016/0022-328X(86)80197-8

M3 - Artikel

AN - SCOPUS:0040047026

VL - 310

SP - 333

EP - 355

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 3

ER -