Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d-electron count

Westcott, S. A.; Kakkar, Ashok; Stringer, Graham; Taylor, Nicholas J.; Marder, Todd B.

doi:10.1016/0022-328x(90)87268-i

Cited by 192 publications

(138 citation statements)

References 42 publications

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“…(8) and Ru(Ind), (21) have been reported in the literature. It is instructive for our analysis to briefly compare these structures to the corresponding Cp analogues.…”

Section: Resultsmentioning

confidence: 99%

“…The complexes NiCp, and RuCp, were purchased from Aldrich and purified by vacuum sublimation prior to use. Ni(Ind), (7,8) and Ru(Ind), (9) were prepared according to literature procedures. Reacting (PPh,),NiX, (X = C1 and Br) with IndLi (Ind = indenyl and 1-Me-indenyl) furnished the complexes (Ind)Ni(PPh,)X, which were, in turn, reacted with MeMgBr or MeLi to give the methyl derivatives (X = Me).…”

Section: Methodsmentioning

confidence: 99%

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Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Bayrakdarian¹,

Davis²,

Reber³

et al. 1996

Can. J. Chem.

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Abstract:The electronic structures of two types of transition metal indenyl complexes have been studied. The first type, a series of (Ind)Ni(PPh,)X compounds (Ind = indenyl, 1-Me-indenyl; X = C1, Br, Me) was investigated by absorption spectroscopy and Extended Huckel Molecular Orbital calculations. The energy differences between calculated levels are in good agreement with experimental band positions. For example, the lowest energy singlet-singlet band maximum for (Ind)Ni(PPh,)Cl is at 19 500 cm-I and the calculated HOMO-LUMO difference is 19 817 cm-I. For X = Me, the calculated energy difference increases to 21 930 cm-I and the corresponding absorption band is at 22 500 cm-I. The influence of the metal-ligand interactions on the molecular orbitals is discussed. The second category of indenyk'the bis(indeny1) compounds of Ni and Ru, show absorption spectra that are markedly different from those of nickelocene and ruthenocene. For example, in comparison to nickelocene, the first absorption band of Ni(Ind), is 5700 cm-' higher in energy and is more intense by two orders of magnitude; in contrast, the first absorption maximum of Ru(Ind)? is 6600 cm-' lower in energy than observed for ruthenocene. The characteristics and relaxation dynamics of the lowest energy excited states are discussed.Key words: absorption spectroscopy, indenyl, nickel, ruthenium, EHMO analysis.

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“…(8) and Ru(Ind), (21) have been reported in the literature. It is instructive for our analysis to briefly compare these structures to the corresponding Cp analogues.…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Bayrakdarian¹,

Davis²,

Reber³

et al. 1996

Can. J. Chem.

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“…6A) connected to a hexagon in the "belt region" of C 70 fullerene core is slightly longer than the remaining four C-C bonds in the pentagon, a feature known for indenyl iron complexes (Fig. 6B) [16]. Bond alternation found in the six-membered ring next to the Cp moiety is another characteristic of an indenyl complex.…”

Section: Synthesis and Properties Of Bucky Ferrocenementioning

confidence: 88%

Bucky ferrocene. Hybrid of ferrocene and fullerene

Nakamura

2003

Pure and Applied Chemistry

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The idea of "bucky ferrocene" intrigues chemists owing to its aesthetic beauty and to its polarized, extended conjugated system, but the idea has remained hypothetical. The synthesis of close analogs of Fe(C 60 Me 5 )Cp and Fe(C 70 Me 3 )Cp was achieved in two steps from [60] and [70]fullerenes, relying on an oxidative C-H bond activation starting with an iron(I) complex and the corresponding cyclopentadienyl precursors, respectively. The molecules can be regarded as members of a new organometallic conjugated system connected to a graphitic system. Numerous synthetic transformations and self-organization procedures that are known for the parent ferrocenes and fullerenes are expected to be employable toward productive use of the ferrocene/fullerene hybrid molecules in chemistry and materials sciences.

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“…Strong correlations between the indenyl ring junction (C3a, C7a) chemical shift and indenyl distortion have been reported (16,18,30,32,33). AS'3~3i,,7e (AS'3~3a,7;, = (indenyl) -S'7~3a,7,(~a+indenyl-)) has been demonstrated to be a reliable indicator of indene hapticity (16, 18, 32, 33) with values in the range -10 to -40 ppm and +5 to +30 considered diagnostic for q5 and q 3 bonding, respectively (33).…”

Section: Synthesis and Propertiesmentioning

confidence: 97%

“…The homoleptic examples [(indenyl),Co]PF6 (30) and (indenyl),Co (31) serve to delineate bonding extrema observed for cobalt and to illustrate the dependence of indene distortion and hapticity on electronic configuration (32). Structural studies (32) establish that the 19e-Co(I1) indenyl complex significantly distorts towards an q 3 bonding mode. "C NMR data (30,.32, 33) confirm that the 18e-Co(I11) complex, [(indenyl)2Co]PF,, is a "true" q5-indenyl species.…”

Section: Introductionmentioning

confidence: 96%

Synthesis, multinuclear NMR, and solution conformation of (η⁵-indenyl)CoIR_fL complexes (L = CO, P-donor)

Jablonski¹,

Zhou²

1992

Can. J. Chem.

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The preparation, spectroscopic characterization, and conformational analysis of a series of Co(II1) indenyl complexes, (C9H7)CoIRfL (Rf = C3F7. C6F13, L = CO, P-donor), 2-8, are described. "C and ' H NMR parameters are consistent with a slightly distorted -qS-C9H7 coordination. 'H nuclear Overhauser effect difference (nOed) spectra indicate a preferred solution conformation in which the perfluoroalkyl group is trans to the C,,-C,, ring junction.CHET R. JABLONSKI et ZHONCXIN ZHOU. Can. J. Chem. 70, 2544Chem. 70, (1992.On dtcrit la preparation, la caracttrisation spectroscopique et l'analyse conformationnelle d'une sCrie de complexes du Co(II1) indenyle, (C9H7)CoRfL (Rf = C3F7 et C6F13; L = C O et P-donneur), 2-8. Les parametres RMN du 'H et du 13 C sont en accord avec une coordination -q5-C9H7 legerement deformie. Les spectres de difference d'effet Overhauser nucliaire du 'H (deOn) suggerent une conformation privilCgiCe en solution dans laquelle le groupe perfluoroalkyle est trans par rapport 2 la jonction C,,-C7,.[Traduit par la redaction]

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Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d-electron count

Cited by 192 publications

References 42 publications

Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Bucky ferrocene. Hybrid of ferrocene and fullerene

Synthesis, multinuclear NMR, and solution conformation of (η⁵-indenyl)CoIR_fL complexes (L = CO, P-donor)

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Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d-electron count

Cited by 192 publications

References 42 publications

Absorption spectroscopy of (Ind)Ni(PPh3)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)2 (M = Ni, Ru; Ind = indenyl)

Absorption spectroscopy of (Ind)Ni(PPh3)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)2 (M = Ni, Ru; Ind = indenyl)

Bucky ferrocene. Hybrid of ferrocene and fullerene

Synthesis, multinuclear NMR, and solution conformation of (η5-indenyl)CoIRfL complexes (L = CO, P-donor)

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Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Synthesis, multinuclear NMR, and solution conformation of (η⁵-indenyl)CoIR_fL complexes (L = CO, P-donor)