Coupling reactions of alkynes with half-open titanocenes: Agostic (C–C)→Ti interactions in a tetra(alkyne) coupling product with the Ti(C5H5)(c-C8H11) fragment

Harvey, Benjamin G.; Arif, Atta M.; Ernst, Richard D.

doi:10.1016/j.jorganchem.2006.08.086

Cited by 23 publications

(11 citation statements)

References 24 publications

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“…No charge concentration directed to Ti from these close contact carbons was noted, and the electron density, Laplacian of the electron density and energy density for the hydrocarbyl ligand could be interpreted without hint of an interaction with Ti. Related titanium and zirconium complexes, which also result from oligomerization of alkynes such as PhCRCSiMe 3 , show similar metric parameters to 2, [33][34][35] although no additional support for the presence of C-CÁ Á ÁM interactions was presented from either solution NMR spectroscopy or computational investigations. Another well characterized titanium complex related to 2, CpTi{C 8 H 11 (PhCCSiMe 3 ) 2 }(PMe 3 ) 3 (Fig.…”

Section: Main Group Early Transition Metals and Actinidesmentioning

confidence: 99%

Intramolecular C–C agostic complexes: C–C sigma interactions by another name

Étienne

Weller

2014

Chem. Soc. Rev.

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In this comprehensive review the developments in the synthesis, characterization and reactivity of complexes (s-, d- and f-block) in which a C-C single bond interacts with a metal centre are discussed: so called C-CM agostic complexes. Such species are of significant interest with regard to structure and bonding, the activation of C-C single bonds and, thus, catalytic methods of C-C bond formation (or activation). Examples of C-C agostic complexes of early and later transition metals, actinides and group 1 metals are discussed, along with C-C agostic interactions in metallacyclobutanes. Examples of Si-Si∙∙∙M, B-C∙∙∙M and B-B∙∙∙M agostic interactions are also presented. Throughout, the structural, spectroscopic and computational markers that indicate the likely presence of a C-C∙∙∙M agostic interaction in a complex are highlighted.

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Section: Main Group Early Transition Metals and Actinidesmentioning

confidence: 99%

Intramolecular C–C agostic complexes: C–C sigma interactions by another name

Étienne

Weller

2014

Chem. Soc. Rev.

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“…The analogous M···C–C σ-complexes (intra- or intermolecular) are of considerable interest with regard to the cleavage and formation of carbon–carbon bonds using transition metals, − processes of significant relevance to organic synthesis and petroleum research. Despite this, examples of M···C–C σ-complexes are rare compared to M···HC, and limited to intramolecular systems, − as kinetically such complexes are disfavored due to the relative inaccessibility and orbital directionality associated with the C–C bond compared with C–H . We recently reported the synthesis of a rhodium complex with a well-defined intramolecular σ-C–C interaction, [Rh(BINOR-S)(P i Pr 3 )][BAr F 4 ] ( 1 , BINOR-S = 1,2,4,5,6,8-dimetheno- S -indacene and Ar F = C 6 H 3 (CF 3 ) 2 ). , This complex has a {Rh(P i Pr 3 )} + fragment coordinated to a saturated organic ligand (BINOR-S) through a metallacyclobutane ring and σ-C–C interaction from a cyclopropane unit (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

C–C Activation in the Solid State in an Organometallic σ-Complex

2011

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Herein is reported the synthesis, by a solid-state reaction from [Ir(NBD)(2)(P(i)Pr(3))][BAr(F)(4)], of the first example of a C-C σ-complex with iridium, [Ir(BINOR-S)(P(i)Pr(3))][BAr(F)(4)]. This compound is unique in that in the solid state it undergoes reversible activation of the C-C single bond that interacts with the metal center, establishing a temperature-dependent equilibrium between Ir(III) C-C σ/Ir(V) bis-alkyl complexes. This process has been interrogated by variable-temperature X-ray diffraction, NMR spectroscopy, and DFT calculations.

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“…Subsequently, an even more complicated tetraalkyne coupling product was isolated, in the form of 6 (Figure ) . Although it was isolated as a byproduct with 4 , it can actually best be imagined to derive from 5 through the addition of another alkyne equivalent, suggesting that the reaction leading to 4 also produced some 5 as well.…”

Section: Alkyne‐derived C–c Agostic Complexesmentioning

confidence: 99%

Transition‐Metal Complexes with (C–C)→M Agostic Interactions

Harvey

Ernst

2017

Eur J Inorg Chem

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The coordination of sigma bonding electron density to a Lewis acid was for some time largely the domain of boron hydride chemistry. Subsequently it was found that C-H bonds could undergo intramolecular coordination to metal centers, forming what are now known as "agostic bonds" and "agostic complexes". Thereafter, even the H-H bond in molecular hydrogen was found to be capable of coordination, leading to what are commonly referred to as "sigma complexes". Eventually, coordination by much more shielded C-C bonds was estab-[a] US Navy, Naval inorganic chemistry from the University of Utah in 2005, studying with Professor Richard D. Ernst. His graduate studies were focused on the synthesis and characterization of early-transition-metal organometallic cage structures and metallacyclobutanes. Many of the compounds studied in his research exhibited unique C-C agostic bonding interactions. His current areas of interest include catalysis, advanced biofuels, high-temperature thermosetting resins, and green chemistry. Richard D. Ernst is a Professor of Chemistry at the University of Utah. He received his B.S. degree in chemistry from the University of California in Berkeley in 1973 and his Ph.D. degree in inorganic chemistry from Northwestern University in 1977. His major areas of interest include organometallic chemistry, particularly of metal-pentadienyl compounds, coordination chemistry, and catalysis of the Fischer-Tropsch and Water Gas Shift reactions.

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Coupling reactions of alkynes with half-open titanocenes: Agostic (C–C)→Ti interactions in a tetra(alkyne) coupling product with the Ti(C5H5)(c-C8H11) fragment

Cited by 23 publications

References 24 publications

Intramolecular C–C agostic complexes: C–C sigma interactions by another name

Intramolecular C–C agostic complexes: C–C sigma interactions by another name

C–C Activation in the Solid State in an Organometallic σ-Complex

Transition‐Metal Complexes with (C–C)→M Agostic Interactions

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