The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2012

Herndon, James W.

doi:10.1016/j.ccr.2014.02.026

Cited by 21 publications

(6 citation statements)

References 1,052 publications

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“…Examples include direct C–H activation of functionalized ketones by metal centers ,,,, and activation of alkynes for metallafurans. ,,,,,,,,, Interestingly, the formation of metallafurans in this work involve not only the substrate phenyl-ynone HCC(CO)Ph but also the alcoholic solvent ROH. A plausible mechanism for the formation of these metallafurans is depicted in Scheme : interaction between the metal center and phenyl-ynone first gives a metal–phenyl-ynone π-intermediate, which subsequently undergoes 1,2-hydrogen shift to give a metal–vinylidene species . The electrophilic C α of the vinylidene is then attacked by the nucleophile RO – originated from the alcoholic solvent ROH, ,,,, leading to a C ∧ O moiety, which has suitable geometry to coordinate to M via both C and O atoms.…”

Section: Resultsmentioning

confidence: 99%

“…Activation of alkynes for functional and novel organic products by transition-metal complexes is one of the most important topics in organometallic chemistry . It is well documented that alkynes generally interact with d6-transition-metal centers through the formation of reactive yet sometimes isolable metal–vinylidene intermediates, which can further transform into other carbon-rich organometallic species including metal–acetylide, −acyl, −allenylidene, −alkoxycarbene, and −carbyne complexes, depending on the functionality of the alkynes and the reactants available in the reaction mixture. , …”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Spectroscopic and Theoretical Studies of Ruthenafuran and Osmafuran Prepared by Activation of Ynone in Alcohol

et al. 2015

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Ruthenafuran and osmafuran monocationic complexes [Ru([14]aneS4)(C ∧ O)] + or [M(bpy) 2 (C ∧ O)] + (C ∧ O = anionic bidentate chelate [C(OR)CHC(Ph)O] − ; [14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane; M = Ru, Os; bpy = 2,2′-bipyridine) have been prepared from reactions between phenylynone HCC(CO)Ph and [Ru ([14]aneS4)Cl 2 ] or [M-(bpy) 2 Cl 2 ] in alcoholic solvents ROH. The formation of metal− vinylidene intermediate, followed by nucleophilic attack by RO − , and carbonyl group coordination to the metal center are believed to be the key steps in the formation of these metallafurans. The nature of the anionic C ∧ O ligand was investigated by electrochemical, spectroscopic, and theoretical means. ■ INTRODUCTIONActivation of alkynes for functional and novel organic products by transition-metal complexes is one of the most important topics in organometallic chemistry. 1 It is well documented that alkynes generally interact with d6-transition-metal centers through the formation of reactive yet sometimes isolable metal−vinylidene intermediates, which can further transform into other carbon-rich organometallic species including metal− acetylide, −acyl, −allenylidene, −alkoxycarbene, and −carbyne complexes, depending on the functionality of the alkynes and the reactants available in the reaction mixture. 2, 3 Our group has been scrutinizing the reactivity between a variety of organic substrates and structurally well-defined d6-transition-metal complexes, and the spectroscopic properties of the derived organometallic complexes. 4 As an extension of this research direction, we now present the reactivity of a specific type of alkyne, phenyl-ynone HCC(CO)Ph, toward [Ru([14]aneS4)Cl 2 ] and [M(bpy) 2 Cl 2 ] (M = Ru and Os; [14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane; bpy = 2,2′-bipyridine) in alcoholic solvents ROH. Our results reveal that the resultant products are metallafuran monocationic complexes [Ru([14]aneS4)(C ∧ O)] + and [M(bpy) 2 (C ∧ O)] + , where C ∧ O represents an anionic bidentate [C(−OR)CHC(−Ph) O] − chelate. It is worth mentioning that metallafuran and other members of metallacycles have received extensive attention in the field of organometallic and theoretical chemistry, 5,6 and the reactivity reported in this work may represent a general synthetic approach for different metallafurans. Moreover, the electronic properties of the ruthenafurans and osmafuran have been probed by electrochemical, spectroscopic, and theoretical studies. ■ RESULTS AND DISCUSSION Synthesis and Characterizations. Ruthenafuran and osmafuran monocationic complexes 1−3 have been prepared in high yield (50−80%) from reactions between phenyl-ynone HCC(CO)Ph and metal precursors [Ru([14]aneS4)Cl 2 ] or [M(bpy) 2 Cl 2 ] (M = Ru, Os) in alcoholic solvents (Scheme 1).These metallafuran complexes are air stable in both solution and solid forms. The alkoxy group attached to the C α is determined by the alcoholic solvent used (cf. synthesis of 1 and 1′). The carbenoid character for the M−C bonds is indicated by the low-field 13 C NMR ...

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Spectroscopic and Theoretical Studies of Ruthenafuran and Osmafuran Prepared by Activation of Ynone in Alcohol

et al. 2015

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“…Lithiations of 2,5-dibromo heterorings ( 5 – 7 ) at −40 °C followed by reaction with tris(8-nonenyl)chlorosilane ( 8 ) afforded the corresponding 1,4-bis(tri-8-nonenyl)silyl heterorings 9 – 11 . Ring-closing metathesis (RCM) ,− of the bissilyl heterorings 9 – 11 under presence of Grubbs’ first generation catalyst and subsequent hydrogenation at 3 atm of hydrogen with Pd/C as a catalyst afforded a mixture of the cage, corresponding noncage isomer, and polymers. The cages ( 1 – 3 ) and noncage isomers ( 1i – 3i ) were isolated from the reaction mixture by preparative gel permeation chromatography (GPC) and identified by NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Molecular Gyrotops with a Five-Membered Heteroaromatic Ring: Synthesis, Temperature-Dependent Orientation of Dipolar Rotors inside the Crystal, and its Birefringence Change

Masuda

Arase

Inagaki

et al. 2016

Crystal Growth & Design

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Three-dimensional arrays of dipolar rotors were constructed as single crystals of molecular gyrotops, which are macrocage molecules with a bridged dipolar rotor. In this study, we synthesized novel molecular gyrotops with a five-membered heteroring, i.e., furan-diyl (1), thiophene-diyl (2), and selenophene-diyl (3), and investigated the temperature-dependent orientation and rotation of the dipolar rotors inside the crystal. Unfortunately, furan derivative 1 did not crystallize; however, crystal structures of the other molecular gyrotops, i.e., 2 and 3, showed three-dimensional arrays of dipolar rotors. Thermal order−disorder transitions of the dipolar rotor orientation inside the crystal were observed in 2 and 3 with the transition temperature in selenophene derivative 3 being lower than that of thiophene derivative 2. This may be ascribed to subtle differences in the molecular structure, e.g., the intersection angle between two Si−C(aryl) bonds corresponding to the rotation axis. In accordance with the thermal change of the crystal structure, temperature-dependent optical properties of a single crystal were observed by analysis of birefringence of the crystal.

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“…The latest addition to the library of alkyl-substituted terminal borylene complexes is the bulky aryl-substituted chromium borylene complex [(OC) 5 Besides the Lewis-base-induced coupling chemistry analogous to that of the manganese system, complex 25 has also been found to carry out reductive borylene−carbonyl coupling in the presence of a strong reducing agent. 66 The reaction of 25 with 2 equiv of potassium graphite leads to the quantitative formation of 26 as a red solid.…”

Section: ■ Reductive Couplingmentioning

confidence: 99%

Reactivity of Transition-Metal Borylene Complexes: Recent Advances in B–C and B–B Bond Formation via Borylene Ligand Coupling

Braunschweig

Shang

2015

Inorg. Chem.

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Terminal borylene complexes of group 6-10 metals have been prepared through a number of synthetic strategies, displaying a wide structural diversity with numerous coordination modes of the borylene ligand [:BR]. Earlier, amino-substituted borylenes were found to serve as borylene ligand transfer reagents to a range of organic and organometallic substrates. In contrast, aryl- and alkyl-substituted borylenes display metathesis behavior when combined with ketones. Recent studies on these complexes revealed new reactivity patterns involving borylene-borylene and carbonyl-borylene ligand coupling. Herein a brief account on the recent progress of these borylene ligand coupling reactions made in our laboratories is provided. These reactions offer unprecedented alternative methods for electron-precise B-B and B-C bond formation.

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The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2012

Cited by 21 publications

References 1,052 publications

Synthesis, Spectroscopic and Theoretical Studies of Ruthenafuran and Osmafuran Prepared by Activation of Ynone in Alcohol

Synthesis, Spectroscopic and Theoretical Studies of Ruthenafuran and Osmafuran Prepared by Activation of Ynone in Alcohol

Molecular Gyrotops with a Five-Membered Heteroaromatic Ring: Synthesis, Temperature-Dependent Orientation of Dipolar Rotors inside the Crystal, and its Birefringence Change

Reactivity of Transition-Metal Borylene Complexes: Recent Advances in B–C and B–B Bond Formation via Borylene Ligand Coupling

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