Reactivity of iron tricarbonyl cycloheptatrienide: synthesis of metal carbonyl ditropylium complexes (C14H14FeM(CO)6) (M = Fe, Cr, Mo, W)

doi:10.1016/S0022-328X(00)89318-3

Journal of Organometallic Chemistry

Volume 97, Issue 3, 23 September 1975, Pages C46-C48

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Abstract

Reaction of [C₇H₇Fe(CO)₃] (I) with allyl halides gives as the final product (OC)₃ FeC₇H₇C₇H₇Fe(CO)₃, which shows a different stereochemistry from the similar mixed (OC)₃ FeC₇H₇C₇H₇M(CO)₃ derivatives obtained by reaction of I with [η-C₇H₇Fe(CO)₃]⁺ (M = Cr, Mo, W).

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H. Maltz et al.
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Cited by (30)

Kohlenwasserstoffverbrückte complexe. XXVI. Reaktionen von anionischen Aromatenkomplexen [(OC)<inf>3</inf>Cr(Ar)]- mit metallorganischen Elektrophilen.
1992, Journal of Organometallic Chemistry
The addition of [(η⁷ -C₇H₇)M(CO)₃]⁺, [(η⁶-C₆H₅)Mn(CO)₃]⁺ and (η⁵-C₅H₅)Fe(η⁵- C₅H₄COCl) to deprotonated benzene, benzthiophene, indene, fluorene and diphenylmethane coordinated to tricarbonyl chromium proceeds with CC coupling and gives the hydrocarbon-bridged complexes (OC)₃Cr(μ-η⁶:n⁶-C₇H₇C₇H₇)M(CO)₃ (1a, b) (M = Cr, Mo), (OC)₃Cr(μ-η₆:η₅-C₆H₅C(O)C₅H₄)Fe(η⁵-C₅H₅) (2), (OC) ₃Cr(μ-η⁶:η⁶-C₈H₅SC₇H₇)Mo(CO)₃ (3), (OC)₃Cr(μ-η⁶:η⁵-C₈H₅S C₆H₆)Mn(CO)₃ (4) (OC)₃Cr(μ-η⁶:η⁶-C₉H₇C₇H₇)Mo(CO)₃ (5), (OC)₃Cr(μ-η ⁶:η⁶-C₁₃H₉C₇H₇)M(CO)₃ (6a, b, c) and (OC)₃Cr(μ-η⁶:η⁶-C₁₃H₁₁ C₇H₇)M(CO)₃ (7a, b, c) (M = Cr, Mo, W).
Die Addition von [(η⁷-C₇H₇)M(CO)₃]⁺, [(η⁶-C₆H₆)Mn(CO)₃] und (η⁵-C₅H₅)Fe(η⁵-C₅H₅ COCl) an die deprotonierten, koordinierten Benzol-, Benzothiophen-, Inden-, Fluoren- und Diphenylmethan-Liganden in Tricarbonylchromverbindungen führt unter CC-Kupplung zu den Kohlenwasserstoffverbrückten Komplexen (OC)₃Cr(μ-η⁶:η⁶-C₆H₅C₇H ₇)M(CO)₃ (1a, b) (M = Cr, Mo), (OC)₃Cr(μ-η⁶:η₅-C₆H₅C(O)C₅H₄)Fe(η⁵-C₅H₅) (2), (OC)₃Cr(μ-η₆:η₆-C₈H₅SC₇H₇)Mo(CO)₃ (3), (OC)₃Cr(μ-η⁶:η⁵-C₈H₅ SC₆H₅)Mn(CO)₃ (4), (OC)₃Cr(μ-η⁶:η⁶C₉H₇C₇H₇)Mo(CO), (5), (OC)₃Cr(μ-η ⁶:η⁶-C₁₃H₉C₇H₇)M(CO)₃ (6a, b, c) and (OC)₃Cr(μ-η⁶:η⁶-C₁₃H₁₁C ₇H₇)M(CO)₃ (7a, b, c) (M = Cr, Mo, W).
Cycloheptatrienyl-bridged heterobimetallic complexes: synthesis and reactivity of (μ-C<inf>7</inf>H<inf>7</inf>)Fe(CO)<inf>3</inf>Ir(CO)<inf>2</inf>
1988, Journal of Organometallic Chemistry
Stereocontrolled acylation of (η4-cycloheptatriene)iron tricarbonyl
1986, Tetrahedron Letters
Interaction of organometallic moleties with carbanions and other electron-rich centers
1983, Journal of Organometallic Chemistry
In this review, I cite literature data which suggest that polyhapto organometallic groups generally provide effective stabilization of β-carbanions through interactions summarized by
. These interactions are also discernible in neutral compounds
having electron-donor groups X = OH, OR, NR₂, etc. The same interaction is responsible for the exo stereochemistry generally observed in deprotonation reactions of alkyl-substituted organometallics, and in electrophilic attacks on double conjugated with organometallic groups, the reverse reaction. And it is responsible for the instability of many η¹-organometallics having acidic β-hydrogens. Wider recognition of the general ability of organometallic groups to stabilize carbanions should lead to broader synthetic exploitation of organometallic compounds.
Hetero- and homo-nuclear bimetallic ruthenol complexes by dehydrogenative metallacyclization of Ru(CO)<inf>3</inf>(bi-1,7-cyclooctadienyl), preparation and x-ray structure of Fe(CO)<inf>3</inf>(C<inf>16</inf>H<inf>22</inf>), RuFe(CO)<inf>6</inf>(C<inf>16</inf>H<inf>22</inf>) and Ru<inf>2</inf>(CO)<inf>6</inf>(C<inf>16</inf>H<inf>20</inf>)
1983, Journal of Organometallic Chemistry
The reaction of M₃(CO)₁₂ (M = Ru, Fe) with excess bi-2,7-cyclooctadienyl (C₁₆H₂₂) 1 gave a mononuclear complex M(CO)₃(1,2,1′-2′-η⁴-C₁₆H₂₂), 2a (M = Ru) or 3a (M = Fe), in good yield. Treatment of 2a with Fe₃(CO)₁₂ or reaction of 3a with Ru₃(CO)₁₂ gave the heterobimetallic complex RuFe(CO)₆(C₁₀H₂₂) consisting of a ruthenacyclopentadiene unit coordinated to an Fe(CO)₃ fragment, as confirmed by ¹H NMR and X-ray studies. The corresponding homobimetallic complex Ru₂(CO)₆(C₁₆H₂₂) was obtained from the 1:1 reaction of 2a with Ru₃(CO)₁₂, while the direct reaction of 1 with Ru₃(CO)₁₂ gave Ru₂(CO)₆(C₁₆H₂₀) preferentially with a loss of two hydrogen atoms. The pathway for formation of these bimetallic complexes was interpreted as a dehydrogenative metallacyclization followed by hydrogen transfer.
Chromium Compounds with η2-η8 Carbon Ligands
1982, Comprehensive Organometallic Chemistry

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Journal of Organometallic Chemistry

Abstract

References (5)

Inorg. Chim. Acta

Chem. Commun.

Cited by (30)

Kohlenwasserstoffverbrückte complexe. XXVI. Reaktionen von anionischen Aromatenkomplexen [(OC)<inf>3</inf>Cr(Ar)]<sup>-</sup> mit metallorganischen Elektrophilen.

Cycloheptatrienyl-bridged heterobimetallic complexes: synthesis and reactivity of (μ-C<inf>7</inf>H<inf>7</inf>)Fe(CO)<inf>3</inf>Ir(CO)<inf>2</inf>

Stereocontrolled acylation of (η<sup>4</sup>-cycloheptatriene)iron tricarbonyl

Interaction of organometallic moleties with carbanions and other electron-rich centers

Chromium Compounds with η<sup>2</sup>-η<sup>8</sup> Carbon Ligands

Preliminary communicationReactivity of iron tricarbonyl cycloheptatrienide: synthesis of metal carbonyl ditropylium complexes (C14H14FeM(CO)6) (M = Fe, Cr, Mo, W)

Abstract

Inorg. Chim. Acta

Chem. Commun.

Preliminary communication
Reactivity of iron tricarbonyl cycloheptatrienide: synthesis of metal carbonyl ditropylium complexes (C₁₄H₁₄FeM(CO)₆) (M = Fe, Cr, Mo, W)