A novel 16-electron cyclooctenyliron(II) cation

Ittel, Steven D.; Van-Catledge, F. A.; Tolman, Chadwick A.; Jesson, J. P.

doi:10.1021/ja00472a061

Cited by 42 publications

(42 citation statements)

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“…Teuben and coworkers (20) have reported the COH activation of acetonitrile via a -bond metathesis using Cp* 2 LnCH(SiMe 3 ) 2 . Jesson and coworkers (21) have also documented the formation of the cyanomethyl hydride as a result of activation of acetonitrile using (dmpe) 2 M(Np)H (M ϭ Fe, Ru; Np ϭ 2-naphthyl). The scission of the COCN bond of acetonitrile has also been reported by Parkin and coworkers (22), Brookhart and coworkers (23,24), Nakazawa et al (25), and Jones and coworkers (26).…”

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The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

Vetter

Rieth

Jones

2007

Proc. Natl. Acad. Sci. U.S.A.

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O rganometallic complexes of the cyclopentadienyl (Cp) and trispyrazolylborate (Tp) type have been shown to activate a variety of COH bonds in alkanes and arenes (1-9). However, studies on the activation of alkanes and arenes containing reactive functional groups have received far less attention in the literature. Hartwig and coworkers (10-12) have been successful in the hydroborylation of mono-and disubstituted arenes using transition metal catalysts. The borylation of the arene ring is believed to occur after oxidative addition of the ring COH bond without interference of reaction with the functional group. Smith (13,14) has even shown that haloarenes can be borylated and functionalized without affecting the carbon-halogen bond. Although numerous examples are presented for the functionalization of substituted arenes (15), the functionalization of alkanes containing reactive functional groups is somewhat restricted, perhaps because some of the functional groups on the alkanes are more reactive toward the catalysts and do not allow for COH activation. In addition, some functional groups (e.g., OH) are known to make the adjacent COH bonds more reactive in alkanes (16).We recently reported the activation of 1-, 2-, and 3-chloropentanes using a trispyrazolylborate rhodium complex (17). It was determined that the [TpЈRh(L)] fragment did not oxidatively cleave the COCl bond of the chloroalkane, as would have been expected given the relative bond strengths of COH (Ϸ100 kcal) vs. COCl (80 kcal) bonds (18) and the literature precedence that exists for the oxidative addition of COCl bonds to Rh(I) and Ir(I) metal systems (15,19). Surprisingly, the [TpЈRh(L)] fragment reacted exclusively with the terminal COH bonds of the alkane to give the substituted haloalkyl hydride complex. Here, we extend the investigation of the activation of hydrocarbon COH bonds to include substrates containing the nitrile functional group (OC'N).The COH bond activation of acetonitrile has been documented in the past. Teuben and coworkers (20) have reported the COH activation of acetonitrile via a -bond metathesis using Cp* 2 LnCH(SiMe 3 ) 2 . Jesson and coworkers (21) have also documented the formation of the cyanomethyl hydride as a result of activation of acetonitrile using (dmpe) 2 M(Np)H (M ϭ Fe, Ru; Np ϭ 2-naphthyl). The scission of the COCN bond of acetonitrile has also been reported by Parkin and coworkers (22), Brookhart and coworkers (23, 24), Nakazawa et al. (25), and Jones and coworkers (26). Of particular interest is the work by Brookhart using a similar Cp*Rh(PMe 3 ) system (23), which is known to undergo COH bond activation in the presence of alkanes and arenes (3,27). However, in the presence of nitriles and triphenylsilane, the complex promotes the cleavage of the COCN bond.To demonstrate the diversity of nitrile reactivity with low valent metals, our group has also investigated the reactions of aromatic, allylic, and alkyl nitriles using [(dippe)NiH] 2 (28-30). In these studies, 2 coordination of the CN bond to the Ni metal cent...

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The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

Vetter

Rieth

Jones

2007

Proc. Natl. Acad. Sci. U.S.A.

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“…This complex, of which the structure was determined by X-ray analysis, proved to be an excellent one-component catalyst in the reaction of butadiene and C02. -Isoprene and piperylene can be linked up with butadiene and carbon dioxide yielding new &lactones (32,34,36). The insertion of carbon dioxide takes place at tho ally1 group which is formed by the butadiene.…”

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Steuerungsmöglichkeiten bei der übergangsmetall‐katalysierten Umsetzung von 1,3‐Dienen mit Kohlendioxid

Behr

Juszak

et al. 1986

Chem. Ber.

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Die Umsetzung von Butadien mit Kohlendioxid fuhrt bei Einsatz homogener Palladium-, Ruthenium-und Nickelkomplex-Katalysatoren in Ausbeuten bis zu 59% zum Cg-Lacton 2-EthyIiden-6-hepten-S-olid (3). Possibilities of Cootroliog Transition Metal-eatalyzed Reactions of 1,SDienes with Carbon DioxideThe reaction of butadiene with carbon dioxide using homogeneous palladium, ruthenium, and nickel catalysts affords the Cg-lactone 2-ethyIidene-6-hepten-S-olide (3) in yields up to 59%. In contrast, rhodium catalysts give rise to the formation of the C,,-lactone 2-ethyl-2,4,9-undecatrien-4-olide (10) by connection of three molecules of butadiene with carbon dioxide. The Cj3-lactone can also be synthesized by the rhodium-catalyzed reaction of the C9-lactone with butadiene. -Trialkylphosphines containing a CHR2-group bound to the phosphorus and phosphorous or arsenic ylides proved to be extraordinarily effective and selective ligands in the synthesis of the Cg-lactone. This effect is interpreted by an activation of carbon dioxide by means of the ligand. In the reaction of butadiene with COa ally1 and carboxylate complexes of the transition metals are proposed to be the mechanistic intermediates. In fact, the carboxylate complex bis(2-ethylidene-4,6-heptadienoato)bis(triisopro-

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“…[1] Among the above-mentioned insertion reactions, important roles are played by metal-hydride, [5,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] metal-carbon, [5,9a,19,23-32] and metal-nitrogen bonds. [5,9a,28,33-37] A variety of metals have been used in different oxidation states, including a few examples of iron complexes with phosphane [38][39][40][41][42][43][44][45] and nitrogen ligands. [46][47][48][49][50][51][52] There is a great interest in gaining knowledge about the insertion reactions of CO 2 into elemental M-E bonds for a possible extension to systems with steps relevant to catalytic reactions.…”

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Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO₂

2015

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New iron(II) compounds with N-donor ligands [2,2′-bipyridine (bpy) and 2-(2-pyridyl)ethylamine (pyea)] were synthesized, and their reactivity with carbon dioxide was investigated. The reactions of Fe(bpy)(pyea)Cl2 (1) with CO2 (0.9 MPa) afforded the carbamato derivative Fe(bpy)(pyea-CO2)Cl2 (2), which reacted with CH3Li to afford the monomethyl carbamato complex Fe(bpy)(pyea-CO2)ClCH3 (3), an example of a carbamato species that is stable over a carboxylato moiety. Fe[(bpy)(pyea)](CH3)2 (4), obtained by reaction of 1 with CH3Li, was treated with CO2 (0.3-0.5 MPa) to afford the dicarboxylato species Fe[(bpy)(pyea)](O2CCH3)2 (5), which provides evidence of normal double insertion of CO2 into the Fe-C bond. The reaction of 5 with HCl afforded 1 and CH3-CO2H, which confirmed the mode of bonding of the -O2CCH3 moiety to the Fe center. To verify the preference of insertion of CO2 into the Fe-C or the Fe-N bond, 1 was treated with MeLi (1 equiv.), and Fe(bpy)(pyea)Cl(CH3) (6) was isolated as a low-melting solid. The latter was treated with CO2 (0.5 MPa), and the product of insertion into the Fe-CH3 bond was observed as the only carboxylate (7). The faster insertion into the Fe-CH3 bond is explained by the fact that the N donor is quaternarized upon interaction with the metal center and has no free electrons available to interact with the C acceptor of the cumulene molecule; thus, more-forcing conditions (0.9 MPa) are required for the insertion to occur

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A novel 16-electron cyclooctenyliron(II) cation

Cited by 42 publications

References 4 publications

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

Steuerungsmöglichkeiten bei der übergangsmetall‐katalysierten Umsetzung von 1,3‐Dienen mit Kohlendioxid

Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO₂

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A novel 16-electron cyclooctenyliron(II) cation

Cited by 42 publications

References 4 publications

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

Steuerungsmöglichkeiten bei der übergangsmetall‐katalysierten Umsetzung von 1,3‐Dienen mit Kohlendioxid

Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO2

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Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO₂