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

Research output: Contribution to journal › Article › Research › peer review

Authors

  • Frank Edelmann
  • Peter Behrens
  • Sabine Behrens
  • Ulrich Behrens

External Research Organisations

  • Universität Hamburg
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Details

Original languageGerman
Pages (from-to)333-355
Number of pages23
JournalJournal of Organometallic Chemistry
Volume310
Issue number3
Publication statusPublished - 26 Aug 1986
Externally publishedYes

Abstract

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.

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Übergangsmetall-fulven-komplexe. XXVIII. Reaktionen von (fulven)Cr(CO)3-komplexen und α-ferrocenyl-carbeniumionen mit nukleophilen. / Edelmann, Frank; Behrens, Peter; Behrens, Sabine et al.
In: Journal of Organometallic Chemistry, Vol. 310, No. 3, 26.08.1986, p. 333-355.

Research output: Contribution to journal › Article › Research › peer review

Edelmann F, Behrens P, Behrens S, Behrens U. Übergangsmetall-fulven-komplexe. XXVIII. Reaktionen von (fulven)Cr(CO)3-komplexen und α-ferrocenyl-carbeniumionen mit nukleophilen. Journal of Organometallic Chemistry. 1986 Aug 26;310(3):333-355. doi: 10.1016/0022-328X(86)80197-8
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title = "{\"U}bergangsmetall-fulven-komplexe. XXVIII. Reaktionen von (fulven)Cr(CO)3-komplexen und α-ferrocenyl-carbeniumionen mit nukleophilen",
abstract = "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.",
author = "Frank Edelmann and Peter Behrens and Sabine Behrens and Ulrich Behrens",
year = "1986",
month = aug,
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language = "Deutsch",
volume = "310",
pages = "333--355",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
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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.

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