Reductive Coupling of Fulvenes with Calcium for C2-Symmetric ansa-Metallocenes:  Syntheses and Molecular Structures of trans-Ph2C2H2(η5-C5H4)2Ca(THF)2 and trans-Ph2C2H2(η5-C5H4)2ZrCl2

Kane, Kevin M.; Shapiro, Pamela J.; Vij, and Ashwani; Cubbon, Rachel; Rheingold, Arnold L.

doi:10.1021/om9704399

Cited by 76 publications

(77 citation statements)

References 28 publications

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“…The unsymmetrical steric demand in the fulvene used in this synthesis determines the cis and trans distribution (30:70) of the product. [158] Both of the crystallographically characterized species 70 and trans-71 show evidence of appreciable strain (a = 24.88 and 22.98, b = 9.28 and 12.28 (av.)). Ring-opening reactions of these and related cationic [2]cobaltocenophanes would be expected as these d 6 species are isoelectronic with ferrocenophanes.…”

Section: Metallocenophanes Of Cobaltmentioning

confidence: 99%

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

2007

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The structures, bonding, and ring-opening reactions of strained cyclic carbon-based molecules form a key component of standard textbooks. In contrast, the study of strained organometallic molecules containing transition metals is a much more recent development. A wealth of recent research has revealed fascinating nuances in terms of structure, bonding, and reactivity. Building on initial work on strained ferrocenophanes, a broad range of strained organometallic rings composed of a variety of different metals, pi-hydrocarbon ligands, and bridging elements has now been developed. Such strained species can potentially undergo ring-opening reactions to functionalize surfaces and ring-opening polymerization to form easily processed metallopolymers with properties determined by the presence of the metal and spacer. This Review summarizes the current state of knowledge on the preparation, structural characterization, electronic structure, and reactivity of strained organometallic rings with pi-hydrocarbon ligands and d-block metals.

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Section: Metallocenophanes Of Cobaltmentioning

confidence: 99%

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

2007

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“…Photolysis of 1 with [Co 2 (CO) 8 ] afforded the remarkable tetrametallic dimer [(CO) 2 2 ] 2 (13). The corresponding photochemical reaction of 8 with [Co 2 (CO) 8 ] gave a trimetallic insertion product in high conversion,…”

Section: A C H T U N G T R E N N U N G (M-co) 2 a C H T U N G T R E Nmentioning

confidence: 99%

“…The corresponding photochemical reaction of 8 with [Co 2 (CO) 8 ] gave a trimetallic insertion product in high conversion,…”

Section: A C H T U N G T R E N N U N G (M-co) 2 a C H T U N G T R E Nmentioning

confidence: 99%

“…[44] Although extensive previous studies have shown that [1]ferrocenophanes predominantly undergo ring-opening chemistry at the bridging atom EÀCp bond, recent reports have highlighted that reactivity at the FeÀCp bond can also occur, especially on photoactivation. For example, highly tilted bora [1] 8 ] under photoirradiation to afford products 6 and 7, respectively, through insertion of metal carbonyl fragments into the FeÀCp bond. [12] Miyoshi and co-workers have demonstrated that strained phospha [1]ferrocenophanes (a % 278) undergo unprecedented Fe À Cp bond cleavage upon photoirradiation and, in the presence of donor solvents such as THF, photolytic ROP was detected.…”

Section: Introductionmentioning

confidence: 99%

“…9 ] to give products from Fe À Cp bond cleavage and insertion reactions but with notable differences in behaviour. To provide further insight into these phenomena, we have also examined parallel reactions with [Co 2 (CO) 8 ]. 2.4912(7) S(1)ÀC(1A)…”

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confidence: 99%

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Photoinduced FeCp Bond Cleavage and Insertion Reactions of Strained Silicon‐ and Sulphur‐Bridged [1]Ferrocenophanes in the Presence of Transition‐Metal Carbonyls

Ieong

Chan

Lough

et al. 2008

Chemistry A European J

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The photochemical reactions of the moderately strained sila[1]ferrocenophane [Fe(eta-C(5)H(4))(2)SiPh(2)] (1) and the highly strained thia[1]ferrocenophane [Fe(eta-C(5)H(4))(2)S] (8) with transition-metal carbonyls ([Fe(CO)(5)], [Fe(2)(CO)(9)] and [Co(2)(CO)(8)]) have been studied. The use of metal carbonyls has allowed the products of photochemically induced Fe-cyclopentadienyl (Cp) bond cleavage reactions in the [1]ferrocenophanes to be trapped as stable, characterisable products. During the course of these studies the synthesis of 8 from [Fe(eta-C(5)H(4)Li)(2)TMEDA] (TMEDA=N,N,N',N'-tetramethylethylenediamine) and S(SO(2)Ph)(2) has been significantly improved by a change of reaction solvent and temperature. Photochemical reaction of 1 with excess [Fe(CO)(5)] in THF gave the dinuclear complex [Fe(2)(CO)(2)(mu-CO)(2)(eta-C(5)H(4))(2)SiPh(2)] (9). The analogous photolytic reaction of 8 with [Fe(CO)(5)] in THF gave cyclic dimer [Fe(eta-C(5)H(4))(2)S](2) (10) and [Fe(2)(CO)(2)(mu-CO)(2)(eta-C(5)H(4))(2)S] (11), with the former being the major product. Photolysis of 1 with [Co(2)(CO)(8)] afforded the remarkable tetrametallic dimer [(CO)(2)Co(eta-C(5)H(4))SiPh(2)(eta-C(5)H(4))Fe(CO)(2)](2) (13). The corresponding photochemical reaction of 8 with [Co(2)(CO)(8)] gave a trimetallic insertion product in high conversion, [Co(CO)(4)(CO)(2)Fe(eta-C(5)H(4))S(eta-C(5)H(4))Co(CO)(2)] (14). These reactivity studies show that UV light promotes Fe-Cp bond cleavage reactions of both of the [1]ferrocenophanes 1 and 8. We have found that, whereas the less strained sila[1]ferrocenophane 1 requires photoactivation for Fe-Cp bond insertions to occur, the highly strained thia[1]ferrocenophane 8 undergoes both irradiative and non-irradiative insertions, although the latter occur at a slower rate. Our results suggest that such photoinduced bond cleavage reactions may be general and applicable to other related strained organometallic rings with pi-hydrocarbon ligands.

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Boron-Bridged Group-4ansa-Metallocene Complexes

Shapiro

2001

Eur. J. Inorg. Chem.

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Boron‐bridged group‐4 ansa‐metallocene complexes are newcomers to the field of metallocene‐mediated olefin polymerization catalysis. Because of the Lewis acidity of the boron bridge, it is more reactive than the more common carbon and silicon bridges. It is also more vulnerable to cleavage from the ligand framework by nucleophilic agents. A primary goal of our work is to involve the boron bridge more actively in the reaction chemistry of the metallocene while keeping the bridge intact.

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Reductive Coupling of Fulvenes with Calcium for C₂-Symmetric ansa-Metallocenes: Syntheses and Molecular Structures of trans-Ph₂C₂H₂(η⁵-C₅H₄)₂Ca(THF)₂ and trans-Ph₂C₂H₂(η⁵-C₅H₄)₂ZrCl₂

Cited by 76 publications

References 28 publications

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

Photoinduced FeCp Bond Cleavage and Insertion Reactions of Strained Silicon‐ and Sulphur‐Bridged [1]Ferrocenophanes in the Presence of Transition‐Metal Carbonyls

Boron-Bridged Group-4ansa-Metallocene Complexes

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