Jean Roué

Bio: Jean Roué is an academic researcher. The author has contributed to research in topics: Crystal structure & Carbon–carbon bond. The author has an hindex of 3, co-authored 3 publications receiving 59 citations.

Organic chemistry of dinuclear metal centres. Part 12. Synthesis, X-ray crystal structure, and reactivity of the di-µ-alkylidene complex [Ru2(CO)2(µ-CHMe)(µ-CMe2)(η-C5H5)2]: alkylidene linking

Abstract: Upon treatment with methyl-lithium followed by HBF4·OEt2 a carbon monoxide ligand of the µ-alkylidene complex [Ru2(CO)2(µ-CO)(µ-CMe2)(η-C5H5)2](1) is converted into µ-ethylidyne, giving [Ru2(CO)2(µ-CMe)(µ-CMe2)(η-C5H5)2]+(2). This is deprotonated readily by water to form the µ-vinylidene complex [Ru2(CO)2(µ-CCH2)(µ-CMe2)(η-C5H5)2](3), which quantitatively regenerates (2) with HBF4·OEt2. Addition of NaBH4 to (2) results in hydride attack on µ-CMe to yield the di-µ-alkylidene complex [Ru2(CO)2(µ-CHMe)(µ-CMe2)(η-C5H5)2](4) as cis and trans isomers. The structure of the trans isomer has been established by X-ray diffraction. Crystals are triclinic, space group P, with Z= 2 in a unit cell for which a= 8.474(2), b= 7.802(3), c= 12.989(5)A, α= 99.42(3), β= 96.96(3), and γ= 107.73(3)°. The structure was solved by heavy-atom methods and refined to R 0.026 (R′ 0.031) for 4 092 independent intensities. A ruthenium–ruthenium single bond of 2.701(1)A is symmetrically bridged by ethylidene [mean Ru–C 2.079(3)] and isopropylidene [mean Ru–C 2.107(3)A] ligands to form an approximately planar Ru2C2 ring with a non-bonding Me2C··CHMe distance of 3.20 A. Upon thermolysis the alkylidenes link to evolve Me2CCHMe, Me2CHCHCH2, and Et(Me)CCH2. The absence of C4 and C6 hydrocarbons indicates that the alkylidene coupling occurs intramolecularly, and the electronic and stereochemical requirements of this process are discussed. Unlike mono-µ-alkylidene complexes, [Ru2(CO)2(µ-CO)(µ-CR2)(η-C5H5)2], the cis and trans forms. of (4) do not interconvert thermally below 145 °C, but u.v. irradiation effects a slow trans to cis isomerisation. U.v. irradiation of (4) in the presence of dimethyl acetylenedicarboxylate promotes ethylidene–alkyne linking to form [Ru2(CO)(µ-CMe2){µ-C(CO2Me)C(CO2Me)CHMe}(η-C5H5)2], but with ethyne both of the alkylidenes are lost and the ruthenium–ruthenium double-bonded complex [Ru2(µ-CO)(µ-C2H2)(η-C5H5)2] is produced.

Carbon–carbon bond formation through olefin–methylcarbyne linkage at a diruthenium centre: X-ray crystal structure of [Ru2(CO)(µ-CO){µ-η1,η3-C(Me)C(Me)CH2}(η-C5H5)2]

Abstract: Reaction of [Ru2(CO)2(µ-CO)(µ-CMe)(η-C5H5)2]+ with RCHCH2(R = H or Me) under u.v. radiation provides [Ru2(CO)(µ-CO){µ-η1,η3-C(Me)C(R)-CH2}(η-C5H5)2] which, for RH, may also be obtained by treatment of [Ru2(CO)(C2H4)(µ-CO)2(η-C5H5)2] with MeLi, HBF4 successively; the structure of [Ru2(CO)(µ-CO){µ-η1,η3-C(Me)C(Me)CH2}(η-C5H5)2] has been determined by X-ray diffraction.

Synthesis, X-ray crystal structure and reactivity of the di-µ-carbene complex [Ru2(CO)2(µ-CHMe)(µ-CMe2)(η-C5H5)2]

Abstract: Treatment of [Ru2(CO)2(µ-CO)(µ-CMe2)(η-C5H5)2] with methyl-lithium and HBF4 in succession provides the carbyne–carbene-bridged cation [Ru2(CO)2(µ-CMe)-(µ-CMe2)(η-C5H5)2]+ which may be converted into di-µ-carbene complexes [Ru2(CO)2(µ-CCH2)(µ-CMe2)(η-C5H5)2] and [Ru2(CO)2(µ-CHMe2)(µ-CMe2)(η-C5H5)2]; the latter, whose structure has been determined by X-ray diffraction, releases Me2CCHMe at 200 °C as the major volatile product.

Vinylidene and Propadienylidene (Allenylidene) Metal Complexes

Abstract: Publisher Summary The rapid development of the chemistry of transition-metal complexes containing terminal carbene (A) or carbyne (B) ligands has been followed more recently by much research centered on bridged methylene compounds (C). As often occurs in new and developing areas of chemistry, some confusion about the nomenclature of these complexes has arisen. Protonation or alkylation of several ethynyl–metal derivatives gives the corresponding vinylidene complexes in high yield. Several vinylidene complexes of the group VI metals have been obtained by heating σ–chlorovinyl derivatives with tertiary phosphines, phosphites, arsines, or stibines. Several complexes containing μ -C=CHR ligands have been obtained directly from 1-alkynes and two equivalents (or excess) of an appropriate precurso. A general route to complexes containing propadienylidene ligands is by loss of water or alcohols from suitable carbene or vinylidene precursors, or of oxo or alkoxy functions from ynolate anions. The majority of the chemistry of vinylidene and propadienylidene complexes is concerned with their synthesis and reactions. Vinylidene is one of the best π-acceptors known and is exceeded only by SO 2 and CS. The vinylidene ligand occupies an important place in the sequence of reactions linking a variety of well-known η 1 -carbon-bonded ligands. Metal cluster complexes containing vinylidene ligands have been considered as models of species present when olefins or alkynes are chemisorbed on metal surfaces.

The Methylene Bridge

Abstract: Publisher Summary Organometallic chemistry encountered rapid expansion experienced by the synthesis, spectroscopy, structural chemistry, theory, and reactivity of compounds characterized by terminal carbene (methylene, A) and carbyne (methylidyne, B) functionalities. The chemistry of μ-methylene complexes did not develop as extensively as that of its mononuclear counterparts, the latter being characterized by terminal carbene ligands. As in the bonding of carbenes with single atoms metal, the methylene group has a filled orbital (a 1 ) that can act as a sigma donor to the system. Symmetrical methylene (alkylidene) bridges represent the predominant geometry. Stability against thermolysis and photolysis is one of the striking properties of dimetallacyclopropanes, especially of those involving carbonyl and cyclopentadienyl ligands on the metals. There is so far not a single exception to the rule that a μ-methylene complex is at least as stable as its μ-carbonyl counterpart. Substitution reactions at the methylene bridge have been observed, albeit the yields were quite low suggesting that major side reactions had occurred. The molecular regimes in discrete di- and polynuclear complexes are mostly coordinatively saturated, whereas metal surfaces, especially if they are relatively flat and close-packed, have no coordinatively saturated surface atoms, even in the presence of chemisorbed species. There is an array of well-established analogues of the μ-methylene complexes in which the heavier congeners of carbon adopt bridging positions.