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Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

The stereoelectronic influence of phosphine substituents on the coordination and catalytic properties of phosphinoferrocene carboxamides was studied for the model compounds R2PfcCONHMe (1a-d), where fc = ferrocene-1,1?-diyl and R = i-Pr (a), t-Bu (b), cyclohexyl (Cy; c), Ph (d), using experimental and DFT-computed parameters. The electronic parameters were examined via 1JSeP coupling constants determined for R2P(Se)fcCONHMe (6a-d) and C?O stretching frequencies of the Rh(I) complexes trans-[RhCl(CO)(1-kappaP)2] (7a-d); the steric properties of 1a-d were assessed through Tolman?s ligand cone angles (theta) and solid angles (Omega). Generally, a very good agreement between the calculated and experimental values was observed. Whereas the donor ability of the amidophosphines was found to increase from 1d through 1a,c to 1b, the trends in steric demand suggested by the two parameters differed, reflecting the different spatial properties of the phosphine substituents. In situ NMR studies and catalytic tests on the Suzuki-Miyaura cross-coupling of 4-bromoanisole with a bicyclic 4-tolylborate to give 4-methyl-4?-methoxybiphenyl using [Pd(eta2:eta2-cod)(eta2-ma)] (cod = cycloocta-1,5-diene, ma = maleic anhydride) as a Pd(0) precursor revealed that different Pd-1 species (precatalysts) were formed from different ligands and participated in the reaction. Specifically, the bulky and electron-rich donor 1b favored the formation of [Pd(1b)(ma)], while the remaining ligands provided the corresponding bis-phosphine complexes [Pd(1)2(ma)]. The best results in terms of catalyst longevity and efficacy were observed for ligands 1a,c.

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

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A novel method to synthesize asymmetrical disubstituted ferrocenes

A convenient new method was developed for the preparation of 1?-substituted-1-bromoferrocenes which are important precursors for the preparation of 1?,1?-disubstituted-biferrocenes. This method can also be applied to prepare asymmetrical disubstituted ferrocenes, which are potentially useful materials possessing non-linear optical and liquid crystalline properties.

A novel method to synthesize asymmetrical disubstituted ferrocenes

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Discovery of 1,1′-Dibromoferrocene

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Functionalization of Cp4Fe4(CO)4 with Alkyl, Aryl, and Ferrocenyl Groups and the Preparation of Double Clusters [Cp3Fe4(CO)4(C5H4)] 2 and [Cp3Fe4(CO)4(C5H4)] 2[(C5H4)2Fe]

Reaction of Cp4Fe4(CO)4 (1) with RLi and HBF4 in sequence affords Cp3Fe4(CO)4(C5H4R) (R= Me, Bun, and Ph) in moderate yields. Further sequential PhLi/HBF4 treatment of Cp3Fe4(CO)4(C5H4Ph) produces Cp2Fe4(CO)4(C5H4Ph) 2. On the other hand, 1 reacts with lithium diisopropylamide (LDA) and bromoferrocene sequentially to produce a ferrocenylated cluster [Cp3Fe4(CO)4(C5H 4)][(C5H4)FeCp] (3) and a double cluster [Cp3Fe4(CO)4(C5H4)] 2 (2). A similar LDA/dibromoferrocene treatment with 1 leads to 2, [Cp3Fe4(CO)4(C5H 4)][(C5H4)(C5H4Br)Fe] (4), and a ferrocenyl-bridged double cluster [Cp3Fe4(CO)4(C5H4)] 2[(C5H4)2Fe] (5). The new compounds have been characterized by elemental analysis and IR, mass, and NMR spectroscopy.

Functionalization of Cp4Fe4(CO)4 with Alkyl, Aryl, and Ferrocenyl Groups and the Preparation of Double Clusters [Cp3Fe4(CO)4(C5H4)] 2 and [Cp3Fe4(CO)4(C5H4)] 2[(C5H4)2Fe]

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Palladium-catalyzed arylation of ferrocene derivatives: a convenient high yield route to 1,1′-bis(halophenyl)ferrocenes

The Pd-catalyzed cross-coupling reaction between halobenzenes and ferrocene-1,1′-diboronic acid is reported.Condensation proceeds smoothly to give 1,1′-diphenyl- and 1,1′-bis(halophenyl)-substituted ferrocenes bearing fluoro, chloro and bromo substituents in good yields.An effective synthesis of the intermediate ferrocene-1,1′-diboronic acid is described.

Palladium-catalyzed arylation of ferrocene derivatives: a convenient high yield route to 1,1′-bis(halophenyl)ferrocenes

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

Properties and Exciting Facts About 1,1′-Dibenzoylferrocene

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A facile synthetic route to (eta5-benzoylcyclopentadienyl)metal compounds

A reaction between cyclopentadienylsodium and ethyl benzoate in refluxing THF produces (benzoylcyclopentadienyl)sodium (4) in 70-80percent yield.Subsequent treatment of 4 in ethanol solution with thallium ethoxide affords (benzoylcyclopentadienyl)thallium (3) in nearly quantitative yield.Reactions of 3 with Mn(CO)5Br, Re(CO)5Br, 2 or FeCl2 lead to the respective eta5-benzoylcyclopentadienyl derivatives of these metals, and demonstrate the utility of 3 in organometallic syntheses.Reactions of several of these organometallic ketones with cymantrenyllithium<(eta5-C5H4Li)Mn(CO)3> provide a useful new route to bimetallic compounds.

A facile synthetic route to (eta5-benzoylcyclopentadienyl)metal compounds

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Photolysis of diacylferrocenes and their photo-ligand exchange reactions with 1,10-phenanthroline

The photolysis of 1,1?-diacylferrocenes Fc(COR)2 (Fc = Ferrocenyl, R = CH3,Ph) in the presence of 1,10-phenanthroline (phen) in deoxygenated acetonitrile under irradiation with visible light has been studied. In these photolysis systems the phen has two important roles to play: one is to stabilize the photo-liberated Fe2+ by coordination, and the other is to promote the photolysis through photo-ligand exchange. Under this condition the photoproducts were isolated in definite composition and characterized by single crystal X-ray diffraction, 1H NMR spectroscopy, IR spectroscopy, photolysis-cyclic voltammetry and elemental analysis. The mechanism of the reactions was demonstrated to be charge transfer from metal to acylcyclopentadienyl ring, leading to cleavage of the bond between them. The phen attacks the Fe2+ ion to give the stable tris (1,10-phenanthroline) iron(II) complex cation and the acylcyclopentadienyl ring detaches from the Fe2+ ion, giving the enolate anion in the outer sphere of the complex. Crystallographic data for photoproduct 1, [Fe(phen)3] (C5H4COCH3)2 ¡¤CH3CN ¡¤2H2O: triclinic, space group P-1 (No. 2), a=12.714(4), b=13.125(3), c= 14.946(5) A, alpha=106.45(1), beta=112.13(3), gamma=79.60(2). V=2208(1) A3, R = 0.041, RW = 0.052. Crystallographic data for photoproduct 2, [Fe(phen)3](C5H4COC6H 5)2 ¡¤0.5C6H6 ¡¤H2O: triclinic, space group P-1 (No. 2), a= 12.218 (4), b= 12.440 (3), c= 16.989 (2) A, alpha = 98.56(2), beta= 102.06(2), gamma= 100.98(3), V=2431(2) A3, R = 0.049, RW = 0.057.

Photolysis of diacylferrocenes and their photo-ligand exchange reactions with 1,10-phenanthroline

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CHIRAL LIGANDS USED IN TRANSITION METAL CATALYSTS FOR ASYMMETRIC ADDITION REACTIONS ESPECIALLY HYDROGENATION

Ligands of the formula (I) secondary phosphine-Q-P(=O)HR1 (I) in the form of mixtures of diastereomers or pure diastereomers, in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents; Q is a bivalent bisaryl or bisheteroaryl radical with an axial chiral centre to which the two phosphorus atoms are bonded in the ortho positions to the bisaryl or bisheteroaryl bridge bond, or Q is a bivalent ferrocenyl radical with a planar chiral centre or without a planar chiral centre, to which the phosphorus atom of the secondary phosphine is bonded directly or via a C1-C4-carbon chain to a cyclopentadienyl ring, the -P*(=O)HR1 group is bonded either on the same cyclopentadienyl ring in ortho position to the bonded secondary phosphine or on the other cyclopentadienyl ring; P* is a chiral phosphorus atom, and R1 is a hydrocarbon radical, a heterohydrocarbon radical or a ferrocenyl radical, where R1 is a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

CHIRAL LIGANDS USED IN TRANSITION METAL CATALYSTS FOR ASYMMETRIC ADDITION REACTIONS ESPECIALLY HYDROGENATION

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Asymmetric synthesis of planar chiral 2-mono- and 2,2?-disubstituted 1,1?-bisbenzoylferrocenes

An efficient and flexible asymmetric synthesis of planar chiral 2-mono- and 2,2?-disubstituted 1,1?-bisbenzoylferrocenes 4 and 6 is reported. Key step is a highly diastereoselective ortho-metalation of 1,1?-bisbenzoylferrocene 1 via the corresponding bis-SAMP-hydrazone 2 (de?96%), followed by trapping with various carbon, silicon, phosphorus and sulfur electrophiles. Cleavage of the monosubstituted hydrazones 3 led to monosubstituted ketones 4 (ee?98%). Further ortho-substitution of the hydrazones 3 afforded 2,2?-disubstituted hydrazones 5, which could be cleaved to disubstituted ferrocenyl diketones 6 (ee?99%). The new methodology allows a broad and flexible fine-tuning of ferrocenyl ligands desired in asymmetric catalysis. Ozonolysis or reductive hydrazone cleavage using TiCl3 or SnCl2 were the methods of choice to remove the auxiliary.

Asymmetric synthesis of planar chiral 2-mono- and 2,2?-disubstituted 1,1?-bisbenzoylferrocenes

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1-Ethyl-3-methylimidazolium halogenoaluminate ionic liquids as solvents for Friedel-Crafts acylation reactions of ferrocene

Friedel-Crafts acylations of ferrocene in 1-ethyl-3-methylimidazolium halogenoaluminate ionic liquids, [emim]I-(AlCl3)x are described.3 The effect of varying the “bulk” Lewis acidity of the ionic liquids used as solvents in these reactions and the effect of varying the relative amounts of acylating agent with respect to the amount of ferrocene in these reactions is also described. The use of a variety of different acylating agents in our studies demonstrates the scope of this reaction performed in these ionic liquid systems.

1-Ethyl-3-methylimidazolium halogenoaluminate ionic liquids as solvents for Friedel-Crafts acylation reactions of ferrocene

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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BIS(FERROCENYLPHOSPHINO) FERROCENE LIGANDS USED IN ASSYMETRIC HYDROGENATION REACTIONS

Abstract Compounds of the formula (I) in the form of racemates, enantiomerically pure diastereomers or a mixture of diastereomers, where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 4; n is 0 or an integer from 1 to 3; p is 0 or an integer from 1 to 5; R2 is an aromatic hydrocarbon radical or a C-bonded heterohydrocarbon radical and R3 is an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; R2 and R3 are identical or different and are each an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; R4 is an unsubstituted or C1-C6-alkyl-, C1-C6-alkoxy- or halogen-substituted hydrocarbon radical; and A is a secondary amino group, are ligands for metal complexes which are suitable as catalysts for homogeneous enantioselective hydrogenation.

BIS(FERROCENYLPHOSPHINO) FERROCENE LIGANDS USED IN ASSYMETRIC HYDROGENATION REACTIONS

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion