Exploring reactivity of a bis-sulfonium zirconocene-ate dimer: synthesis of various zwitterionic phosphonium anionic zirconocene complexes

Abstract Formal [3+2] cycloaddition reactions between the bis-sulfonium zirconocene-ate dimer 1a and methylpropiolate, benzaldehyde and carbon disulfide afforded stable zwitterionic phosphonium zirconocene-ate complexes 2–4, respectively, with two orthocondensed five-membered heterocycles. X-ray crystal structure of 4 has been determined. Elemental chalcogens (S, Se, Te) gave rise also to a new variety of five-coordinate zirconium(IV) complexes (5–7) by a formal [3+1] cycloaddition reaction. In these bicyclic zirconates, sulfur is included in a five-membered ring while the second chalcogen is in a four-membered one.

Zirconocen–Benzyme-Mediated Intramolecular Coupling of Bis(alkynyl)phosphane: A Way to Mono- and Tricyclic 1,2-Dihydrophosphetes

SYNTHESIS OF SELENIUM-CONTAINING CROWN ETHERS AND RELATED COMPOUNDS

Abstract The synthesis of the first examples of selenium-containing crown ethers from the benzene diselenolate anion and dichalcogenated ethers is reported. The reaction is highly dependent on the experimental conditions, particularly the concentration. 1H NMR and mass spectrometry were used to confirm the structures of the new compounds.

FIRST EXAMPLES OF DISELENO TWEEZER-LIKE LIGANDS: SYNTHESIS, CHARACTERIZATION AND Pt(II) CYCLOMETALATION

Abstract The synthesis of the first examples of diseleno tweezer-like molecules is described starting from diselenocyanobenzenic or pyridinic compounds and chloronaphthyl or anthryl derivatives. The new diselenides are characterized by mass spectrometry and multinuclear NMR spectroscopy. Starting from naphthyl derivatives, it was unambigously demonstrated for the first time their cyclometalation with Pt(II) to form metalloreceptors.

Zirconocene [Cp2Zr] synthon and benzynezirconocene complexes as tools in main group element chemistry

Abstract Interactions between zirconocene or benzyne zirconocene and unsaturated species incorporating main group elements lead to a variety of new metallaheterocycles. Efficient new methodologies of regiospecific syntheses of mono-, bi-, or tricyclic systems incorporating phosphorus, nitrogen, selenium, antimony, germanium or tin are reported.

A doubly bridged isodicyclopentadienyl zirconium complex: bis{N-(3,5-dimethylphenyl)-N-[(η5-isodicyclopentadien-2-yl)dimethylsilyl]amido-κN}zirconium(II) diethyl ether solvate

Transmetallation of the dilithium salt of (3,5-dimethyphenylamino)(isodicyclopentadienyl)dimethylsilane by treatment with zirconium tetrachloride in a 2:1 ratio leads to the substitution of all four chloride ligands. With the applied stoichiometry, the title complex, [Zr(C(20)H(25)NSi)(2)].C(4)H(10)O, was obtained and crystallized from diethyl ether. X-ray diffraction characterization showed that both isodicyclopentadienyl ligands (alternatively called 4,5,6,7-tetrahydro-4,7-methano-1H-indene) are complexed to the metal on their exo face in a completely stereoselective manner and that they are eta(5)-bonded to the Zr atom.

Functionalized Tri‐ and Tetraphosphine Ligands as a General Approach for Controlled Implantation of Phosphorus Donors with a High Local Density in Immobilized Molecular Catalysts

Supported phosphine ligands are auxiliaries of topical academic and industrial interest in catalysis promoted by transition metals. However, both controlled implantation and controlled conformation of ligands should be achieved to produce immobilized catalysts that are able to structurally “copy” efficient homogeneous systems. We provide herein a general synthetic strategy for assembling a new class of branched tetra- and triphosphine ligands with a unique controlled rigid conformation, and thus providing a high local density of phosphorus atoms for extended coordination to the metal center. We prepared new functionalized cyclopentadienyl (Cp) salts to design polyphosphines that were “ready…

Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: allylation and arylation coupling reactions at 10−1–10−4mol% catalyst loadings of ferrocenyl bis(difurylphosphine)/Pd

Abstract Carbon–carbon(sp2–sp2 and sp1–sp2) and carbon–nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3–C3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10−1–10−4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-don…

Preparation of titanocene and zirconocene dichlorides bearing bulky 1,4-dimethyl-2,3-diphenylcyclopentadienyl ligand and their behavior in polymerization of ethylene

Abstract New metallocene dichlorides [η 5 -(1,4-Me 2 -2,3-Ph 2 -C 5 H) 2 TiCl 2 ] ( 2 ), [η 5 -(1,4-Me 2 -2,3-Ph 2 -C 5 H) 2 ZrCl 2 ] ( 3 ) and [η 5 -(1,4-Me 2 -2,3-Ph 2 -C 5 H)η 5 -(C 5 H 5 )ZrCl 2 ] ( 4 ) were prepared from lithium salt of 1,4-dimethyl-2,3-diphenylcyclopentadiene ( 1 ) and [TiCl 3 (THF) 3 ], [ZrCl 4 ] and [η 5 -(C 5 H 5 )ZrCl 3 (DME)], respectively. Compounds 2–4 were characterized by NMR spectroscopy, EI-MS and IR spectroscopy, and the solid state structure of 3 was determined by single crystal X-ray crystallography. The catalytic systems 3 /MAO and 4 /MAO were almost inactive in polymerization of ethylene at 30–50 °C, however, they exhibited high activity at temperature…

A straightforward copper-free palladium methodology for the selective alkynylation of a wide variety of S-, O-, and N-based mono- and diheterocyclic bromides and chlorides

Abstract High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh3 and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling usin…

Different coordination modes of a 1,1′,2,2′-ferrocenyltetraphosphine: Bi- and tri-dentate behaviour with group 6 and 7 transition metals

The behaviour of 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di(tert-butyl)ferrocene (1), acting as a homoannular or heteroannular ligand, has been studied. Due to the cisoid disposition of the phosphino groups of each ring, different coordination modes are observed. With group 6 metal carbonyls, M(CO)6, the tetraphosphine acts exclusively as a tridentate ligand. In contrast, the reaction with MnCp(CO)3 leads to complexes showing 1,1′ and 1,2 bidentate coordination modes. All these complexes have been characterised by 1H and 31P NMR spectroscopy. The molecular structures of the molybdenum complex [(1)Mo(CO)3] (2b) and the 1,1′ manganese complex [(1)MnCp(CO)] (3) have been established by X-ra…

"Through-space" 31P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: improvement in the determination of the distance dependence of J(P,P) constants

Abstract From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique 31P–31P “through-space” nuclear spin–spin coupling constants (JPP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these JPP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P⋯P distance dependence of coupling constants) is remarkably confirmed, and mathemati…

Antimicrobial Activity of Resveratrol Analogues

Stilbenes, especially resveratrol and its derivatives, have become famous for their positive effects on a wide range of medical disorders, as indicated by a huge number of published studies. A less investigated area of research is their antimicrobial properties. A series of 13 trans-resveratrol analogues was synthesized via Wittig or Heck reactions, and their antimicrobial activity assessed on two different grapevine pathogens responsible for severe diseases in the vineyard. The entire series, together with resveratrol, was first evaluated on the zoospore mobility and sporulation level of Plasmopara viticola (the oomycete responsible for downy mildew). Stilbenes displayed a spectrum of acti…

General route to dissymmetric heteroannular-functionalized ferrocenyl 1,2-diphosphines: selective synthesis and characterization of a new class of tri- and tetrasubstituted ferrocenyl compounds

Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferroceny...

Versatile behavior of conjugated diynes with zirconocene reactive species

Thermal decomposition of Cp2ZrPh2 in the presence of the buta-1,3-diynes RC≡CC≡CR (R = Ph, SiMe3) can lead to seven- or five-membered metallacycles. In both cases a stable benzo-fused seven-membered zirconacyclocumulene arising from a 2-fold insertion of the triple bonds of the dialkyne in the in situ generated zirconocene benzyne is formed. In the case of Me3SiC≡CC≡CSiMe3 a second minor complex is isolated: a 3-alkynyl-substituted zirconaindene arising from a β monoinsertion of one acetylenic function of the conjugated diyne in the zirconocene benzyne. No stable 2-alkynyl-substituted zirconacycle was isolated. This α monoinsertion complex is an intermediate in the exchange of the metalated…

ansa-[(tert-Butylamino)(isodicyclopentadienyl)dimethylsilane]Zr(NMe2)2prepared by an amine-elimination reaction

An amine-elimination reaction was used to obtain the title compound, i.e. (N-tert-butyl-N-[[(1,2,3,3a,7a-eta)-4,5,6,7-tetrahydro-4,7-methano-1H-inden-2-yl]dimethylsilyl]amido-kappaN)bis(N-methylmethanaminato-kappaN)zirconium(IV) or [isodiCpSiMe(2)N-tert-butyl]Zr(NMe(2))(2) (Cp is cyclopentadienyl), [Zr(C(16)H(25)NSi)(C(2)H(6)N)(2)], in very good yield. Treatment of isodiCpHSiMe(2)NH-tert-butyl with Zr(NMe(2))(4) leads to the formation of a yellow solid that can be purified by sublimation. The single-crystal structure of the product shows the exo complexation of the isodicyclopentadienyl ligand to the Zr atom. The Cp portion of this ligand is bonded to the Zr atom in a eta(5) manner, with a …

Titanium isodicyclopentadienide hemimetallocenes for ethylene/styrene copolymerization

Abstract The syndiotactic polymerization of styrene with exo-[(η5-isodiCp)TiCl3] 1/methylalumoxane (MAO; isodiCp=isodicyclopentadienyl) was studied as well as the ethylene/styrene copolymerization with exo-[{η5:η1(N)-isodiCp(SiMe2Nt-Bu)}TiCl2] 2/MAO. These two catalytic systems are stable during polymerization. The half-sandwich titanocene 1 exhibits good syndiospecificity and average activity. The bridged half-sandwich amino complex 2 was found to incorporate styrene into polymer chains at 70 °C. Activity results decrease with increasing styrene concentrations.

ChemInform Abstract: Synthesis of the First Benzodiselenagermoles and One Spirobisdiselenagermole.

Abstract The first examples of compounds R1R2GeSe2C6H4R3 (R1,R2=CH3 C2H5, C3H2, n-C4H9, i-C5H11, Ph, p-CH3Ph. R3=H, CH3, OCH3) were easily obtained (40–80% yield) from electrophilic cleavage of diselenophenylene zirconocenes by dialkyl or diaryl dichlorogermanes. The synthesis of a spirodi-selenagermole was achieved in the same way using germanium tetrachloride. Analytical data, 1H and 77Se NMR. mass spectra are perfectly consistent with the expected structures.

Synthesis ofo-thiatelluraphenylenezirconocenes. X-ray crystal structure of

o-Thiatelluraphenylenezirconocene complexes were obtained in good yield by reaction of dilithiumo-benzenthiatelluride with zirconocene dichlorides. These compounds represent the first examples of heterodichalcogenaphenylene bent metallocences. They were characterized by spectroscopic methods and the effect on the n.m.r. results of stepwise substitution of one and two Te atoms for S is discussed.

The first catalytic method for Heck alkynylation of unactivated aryl bromides (copper-free Sonogashira) in an ionic liquid: 1 mol-percent palladium/triphenylphosphane/pyrrolidine in [BMIM][BF4] as a simple, inexpensive and recyclable system

Herein we report the studies of Heck alkynylation (copper-free Sonogashira) with aryl halides (I, Br, Cl) employing various metallic precursors, tertiary phosphanes and bases in [BMIM][BF4] as the solvent. As a result, we provide the first method that allows the coupling of a large array of substrates, either activated or deactivated bromides in an ionic liquid. Furthermore, the system of highest efficiency is unexpectedly the simplest and cheaper combination that employs [Pd(η3-C3H5)Cl]2/PPh3 at only a 1 mol-% loading with pyrrolidine as the base and in the absence of a copper salt. The coupling of sterically and electronically deactivated bromides bearing different functional groups to ar…

C,N-chelated dicyclopentadienylzirconium complexes and their possible use as hydrogenation catalysts

Abstract In situ generated Cp2Zr(n-Bu)Cl (6) reacts with {2-[(CH3)2NCH2]C6H4}2Pb to form exclusively {2-[(CH3)2NCH2]C6H4}Cp2ZrCl (7), [(CH3)2NCH2]C6H5, butene and elemental lead. The further derivatization of chloride (7) to fluoride (8), hydride (9), methyl derivative (10), and a reduction of 7 are also described. The crystal structures of 7–10 were determined. The catalytic activity of 9 and 10 in hydrogenation of styrene was also preliminarily tested.

1,1′,2,2′-Tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene, a new cisoid arrangement of phosphino groups

Abstract The action of two equivalents of 1,2-bis(diphenylphosphino)-4- tert -butylcyclopentadienyllithium on FeCl 2 led to the corresponding 1,1′,2,2′-tetraphosphinoferrocene. The X-ray structure of this bulky ferrocene is described. The spectroscopic results reveal a conformational chirality with a cisoid disposition of the phosphino groups. The first results about the complexation with representative elements of Group IX and X (Rh, Pd, Ir) are reported.

Resveratrol-Related Dehydrodimers: Laccase-Mediated Biomimetic Synthesis and Antiproliferative Activity

Seven resveratrol-related monomeric stilbenoids were submitted to biomimetic oxidative coupling in the presence of laccase from Trametes versicolor (TvL), and gave racemic dihydrobenzofuran dehydrodimers (±)-15 to (±)-21. These products, after spectral characterization, were submitted to an antiproliferative activity bioassay against SW480 human colon cancer cells. Five racemates were found to be active, and were resolved by chiral HPLC. The pure enantiomers were subjected to circular dichroism measurements to establish their absolute configurations at C-7 and C-8. These enantiomerically pure compounds were submitted to the antiproliferative activity assay towards SW480 cells, and were all …

An easy route to 1-germaindenes via a transmetallation zirconiumgermanium reaction

Abstract Several 1-zirconaindenes ( 4 ) have been obtained easily by heating phenylmethylzirconocene with various symmetrical (R  R′  CH 3 , C 2 H 5 , n-C 3 H 7 , Si(CH 3 ) 3 and unsymmetrical (R  CH 3 , R′  Si(CH 3 ) 3 ) alkynes (RCCR′). Under similar experimental conditions, the ynamine, diethylaminotrimethylsilylethyne, led to a regioselective reaction. From the X-ray structure of the zirconaindene product, the trimethylsilyl group was found close to the zirconium atom. Compounds 4 with germanium tetrachloride afford new 1-germaindenes ( 7 ) characterized by 1 H and 13 C NMR and mass spectrometry, in good yield.

Benzodiselenagermoles and spirobisbenzodiselenagermoles

Synthesis of benzodiselenagermoles and bisbenzodiselenagermoles was carried out by transmetallation group 4 group 14 between diselenophenylenezirconocenes and dialkyl-, diaryl- or alkylaryldichlorogermanes, aryltrichlorogermane or germanium tetrachloride. The new compounds were studied by 1H, 77Se NMR and mass spectrometry. In the case of compounds with substituted phenyl groups, double irradiation and 2D NMR experiments were performed to determine the chemical shifts of the two selenium atoms. The crystal structure of a spirobisbenzodiselenagermole has been established by X-ray diffraction analysis.

Enlarging the family of ferrocenylphosphine dinuclear rhodium complexes: synthesis and X-ray structure of a novel “A-frame”-type trimetallic Rh/Fe/Rh complex

Abstract The symmetrically substituted ligand 1,1 ′ -bis[di(5-methyl-2-furyl)phosphino]ferrocene ( 1 ) has been obtained from the bromophosphine BrP(Fu Me ) 2 and the dilithioferrocene/TMEDA adduct. The quantitative addition of this ferrocene derivative to the tetracarbonyl dimer [(CO) 4 Rh 2 {μ-(S t Bu) 2 }] leads, through decarbonylation, to the dinuclear rhodium complex [(CO) 2 Rh 2 {μ-(S t Bu) 2 }{μ- P , P -Fc[P(Fu Me ) 2 ] 2 }] ( 2 ) in high yield. A X-ray structure [ orthorhombic , space group P 2 1 2 1 2 1 ; a =11.2982(2) A, b =13.3165(3) A, c =27.2687(7) A] and the solution multinuclear NMR characterization are reported, which show that the rare “quasi-closed bridging” A-frame struc…

Metabolism of stilbene phytoalexins by Botrytis cinerea: 1. Characterization of a resveratrol dehydrodimer

Abstract Resveratrol, a grapevine phytoalexin, is metabolized by a laccase-like stilbene-oxidase of Botrytis cinerea, the causal organism for grey mould. Characterization of one major metabolite formed during this degradation process as a resveratrol dehydrodimer allowed us to precize the reaction mechanism of this enzyme on stilbenes.

Structural determinants of resveratrol for cell proliferation inhibition potency: experimental and docking studies of new analogs.

International audience; Resveratrol is the subject of intense research because of the abundance of this compound in the human diet and as one of the most valuable natural chemopreventive agents. Further advances require new resveratrol analogs be used to identify the structural determinants of resveratrol for the inhibition potency of cell proliferation by comparing experimental and docking studies. Therefore, we synthesized new trans/(E)- and cis/(Z)-resveratrol - analogs not reported to date - by modifying the hydroxylation pattern of resveratrol and a double bond geometry. We included them in a larger panel of 14 molecules, including (Z)-3,5,4'-trimethoxystilbene, the most powerful molec…

Production of the Phytoalexin Resveratrol by Grapes as a Response to Botrytis Attack Under Natural Conditions

Le resveratrol (3,5,4'-trihydroxystilbene) est un des mebolites de stress produit par la vigne en reponse a une infection parasitaire ou une blessure. La distribution de cette molecule dans des lesions limitees causees par Botrytis cinerea sur des grappes de raisins a maturite au vignoble a ete etudiee. Le resveratrol est localise principalement dans les fruits sains entourant les zones infectees. Cette reponse localisee contribue a limiter l'extension du pathogene tant que les conditions climatiques lui sont defavorables. Lorsque les conditions deviennent favorables; c'est-a-dire apres une periode humide et chaude, une expansion rapide des lesions est alors observee sur les fruits en depit…

Synthesis and characterisation of a new class of phosphine-phosphonite ferrocenediyl dinuclear rhodium complexes

We previously reported the easy access to mixed ferrocenediyl ligands bearing phosphine and phosphonite moieties. Using this strategy, a new enantiopure phosphine-menthylphosphonite ferrocenediyl has been synthesised. This mixed ligand leads to original unsymmetrical dinuclear rhodium coordination-complexes. One example of this new class of “quasi-close bridging A frame” dinuclear rhodium complexes, fully characterised by multinuclear 1H, 13C, 31P and 103Rh NMR and optical rotation measurements, is presented. Preliminary tests have shown an activity improvement in the hydroformylation of oct-1-ene using the phosphine-menthylphosphonite ferrocenediyl auxiliary compared to known phosphine-pho…

Copper(I) Iodide Polyphosphine Adducts at Low Loading for Sonogashira Alkynylation of Demanding Halide Substrates: Ligand Exchange Study between Copper and Palladium

The prestabilization of copper iodide with a multidentate ferrocenyl phosphine ligand promotes the palladium-catalyzed cross-coupling of demanding halides with phenylacetylene in a selective way. Novel CuI-triphosphine adducts are described in the solid state and in solution. Their use allowed the introduction of the copper iodide cocatalyst in unprecedented low amounts (0.4 to 0.1 mol %) in systems also employing low amounts of “ligand-free” [PdII(η3-allyl)Cl]2 precursor (0.2 to 0.05 mol %). The scope of substrates is reported, and electronically or sterically deactivated bromides were efficiently coupled. Concerning aryl chlorides, electron-poor activated substrates were also coupled usin…

Intramolecular coupling of acetylenic groups of bis(alkynyl)phosphanes and silanes mediated by benzynezirconocene: a route to new mono- and tricyclic heterocycles

Benzo-zirconacyclohexadiene-phospha or silacyclobutene fused ring systems are easily prepared via a benzynezirconocene intermediate by means of thermolysis of Cp 2 ZrPh 2 in the presence of bis(alkynyl)phosphanes or silanes. These polyunsaturated systems are the source of a variety of new mono- or tricyclic heterocycles incorporating either one or two heteroatoms.

On the mechanistic behavior of highly efficient palladium-tetraphosphine catalytic systems for cross-coupling reactions: first spectroscopic and electrochemical studies of oxidative addition on Pd(0)/multidentate ferrocenylpolyphosphine complexes

Electrochemical studies carried out in conjunction with 31P NMR spectroscopy on the palladium(II)/palladium(0) halogeno complexes of the tetraphosphine 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di...

Coupling of Benzynezirconocene with 1,4-Diphenyl-1,3-butadiyne

The thermolysis of diphenylzirconocene in the presence of 1,4-diphenyl-1,3-butadiyne to yield the seven-membered zirconacyclocumulene 1 via the intermediacy of benzynezirconocene is described. This complex has been characterized by an X-ray diffraction study. Additionally, better knowledge of the bonding of the cumulene moiety was achieved by DFT calculations. Cleavage of the Zr−C bonds of 1 with methanol provided the corresponding butatriene 2.

Reactions of titanocene-bis(trimethylsilyl)ethyne complexes with diethynylsilane derivatives

Titanocene complexes [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 4 and 5) react uniformly with siladiynes R 2 2 Si(CCR 1 ) 2 , where R 1 =Ph, and R 2 =Ph or Me, at elevated temperature in hydrocarbon solvents to give the corresponding silacyclobutene-annelated titanacyclobutene complexes, 3-bis(η 5 -cyclopentadienyl)titana-6-diorganylsilabicyclo[2.2.0]hexa-1(2),4(5)-dienes, [(η 5 -C 5 H 5− n Me n ) 2 Ti{R 1 2 C 4 (SiR 2 2 )}]. Products arising from [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 2 (1,3-isomer), 4 and 5) and Me 2 Si(CCCMe 3 ) 2 vary with n : the non-methylated titanocene complex affords a mixture of an analogous silacyclobutene-annelated t…

"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coordination complexes.

Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constan…

Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives

Ferrocenylphosphines added to [Pd(µ-Cl)(η3-C3H5)]2 dimeric precursor produce efficient catalysts to effect the allylic amination of terpenic allylacetates. Particularly convenient are tetrakis(diphenylphosphino)ferrocene and 1,1′-bis(diphenylphosphino)ferrocene, which allow the amination of allylacetates with good to excellent selectivity, and have turnover numbers as high as 80 000, for instance, for the formation of allylaniline. Herein, we report on reactions that selectively transform geranylacetate, nerylacetate, linalylacetate and perillylacetate into the corresponding allylic amines. These preparative methods give facile access to various products of great potential industrial intere…

ChemInform Abstract: Syntheses of Polyfunctionalized Resveratrol Derivatives Using Wittig and Heck Protocols.

In the modified Wittig reaction, Tms is used as a highly valuable protecting group of the phenolic functions of the starting arenes.

Syntheses and properties of some exo,exo-bis(isodicyclopentadienyl)titanium low-valent complexes

Abstract The paramagnetic compounds exo,exo-bis(η5-isodicyclopentadienyl)chlorotitanium(III) (3) and its analogue with trimethylsilyl-substituted isodicyclopentadienide (isodiCp) ligand (4), and the similar pair of diamagnetic exo,exo-bis(isodicyclopentadienyl)[η2-bis(trimethylsilyl)ethyne]titanium(II) complexes 5 and 6 were obtained by common reduction procedures from exo,exo-bis(isodicyclopentadienyl)titanium(IV) dichloride (1) and exo,exo-bis[η5-2-(trimethylsilyl)isodicyclopentadienyl]titanium(IV) dichloride (2), respectively. As indicated by ESR spectroscopy compound 3 is a dimer in the solid state and in frozen toluene glass but monomeric in toluene solution. Compound 4 is monomeric in…

Catalytic Efficiency of a New Tridentate Ferrocenyl Phosphine Auxiliary: Sonogashira Cross-Coupling Reactions of Alkynes with Aryl Bromides and Chlorides at Low Catalyst Loadings of 10-1 to 10-4 mol %.

[structure: see text] The catalytic activity in Sonogashira cross-coupling reactions of alkynes with a variety of aryl halides (including chlorides) using a multidentate ferrocenyl phosphine is presented. The novel mixed ferrocenyl aryl/alkyl triphosphine is thermally stable and insensitive to air or moisture, and its robustness allows aryl alkynylation at 10(-1) to 10(-4) mol % catalyst loadings with TONs up to 250,000. Copper-free coupling using phenylacetylene is also accessible in good yield.

ChemInform Abstract: A Straightforward Copper-Free Palladium Methodology for the Selective Alkynylation of a Wide Variety of S-, O-, and N-Based Mono- and Diheterocyclic Bromides and Chlorides.

Abstract High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh3 and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling usin…

Zirconocene-ate Zwitterionic Complexes: Preparation and X-ray Structure

Structure, properties and comparison of C,N-chelated and amido-stabilized plumbylenes

The molecular structure of {2-[(CH3)2NCH2]C6H4}2Pb (1) in the solid state was determined by X-ray diffraction techniques on a single crystalline material. Bulky amido ligand stabilized complexes [(i-C3H7)2C6H3]NHLi (2) and [(i-C3H7)2C6H3N(Me3Si)]2Pb (3) were synthesized and characterized both in the solid state and solution by 1H, 13C, 15N and 207Pb NMR and XRD techniques. The structure of both C,N-chelated and bulky amido plumbylenes is compared.

Performances of symmetrical achiral ferrocenylphosphine ligands in palladium-catalyzed cross-coupling reactions: A review of syntheses, catalytic applications and structural properties

Abstract Ferrocene derivatives bearing donor atoms led to the generation of several classes of metallo-ligands, which collectively show an impressive diversity of applications, especially in metal-catalyzed modern organic reactions. Based on the impetus provided by the use of the diphosphine 1,1′-bis(diphenylphosphino)ferrocene (dppf) the investigations directed towards the synthesis of new ferrocenylphosphines remain of fundamental and industrial interest. The present review aims to describe the performances in palladium-catalyzed cross-coupling reactions of symmetrical achiral ferrocenylphosphine ligands, mainly diphosphines. We specifically choose to restrict our review efforts to these …

Structural diversity in coordination chemistry of tridentate and tetradentate polyphosphines of Group 6 to 10 transition metal complexes

Abstract Tridentate and tetradentate polyphosphines offer a huge variety of coordination modes to transition metals which lead, depending on the metal, to very different structural features in the resulting complexes. Steric effects being crucial in metal–phosphine complexes reactivity, a good knowledge of the molecular structures of the species is required both in the solid state and in solution. This article reviews from a structural point of view the monometallic and symmetrical homobimetallic complexes of the transition elements of Group 6 to 10 with tridentate and tetradentate phosphines. Concerning the classical triphosphines and tetraphosphines, emphasis was put on advances reported …

Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: a New Concept in Polyphosphane Ligands Evidenced by “Through-Space” Nuclear Spin-Spin Coupling. Application in heteroaromatics arylation by direct C–H activation

The present study deals with the conformational control of the metallocene backbone within ferrocenyl polyphosphane ligands and their performance in the highly topical palladium-catalyzed heteroaromatics arylation by direct C−H activation. New substituted cyclopentadienyl rings were synthesized, which allowed the assembling of original tri- and diphosphanes. The bulky cyclopentadienyl lithium salts diphenylphosphino-3-(triphenyl)methylcyclopentadienyllithium (4) and 1,2-bis(diphenylphosphino)-4-(triphenyl)methylcyclopentadienyllithium (5) were prepared in excellent yield. The assembling of these new hindered cyclopentadienyl salts (Cp) with other Cp fragments was performed in order to prepa…

Direct arylation of heterocycles: the performances of ferrocene-based polyphosphane ligands in palladium-catalyzed C-H bond activation

International audience; The palladium-catalyzed direct arylation of alkylated- furan, thiophene, and thiazole and benzoxazole heterocycles with electronically and sterically deactivated bromoarenes was selectively and efficiently promoted by ferrocenyl polyphosphanes. In this C[BOND]H bond activation reaction of heteroaromatics, the performances of polydentate di-, tri-, and tetraphosphane ligands were compared, showing that the triphosphane 1,1′,2-tris(diphenylphosphino)-4-tert-butylferrocene 3 was the most effective for the coupling. The introduction of more electron-donating (iPr) or electron-withdrawing (furyl) groups on the phosphorus atoms did not improve the ligand performances. The …

Zirconium & Hafnium: Organometallic ChemistryBased in part on the article Zirconium & Hafnium: Organometallic Chemistry by Bernard Gautheron, Roland Broussier, & Philippe Meunierk which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

This review considers the main aspects of organometallic chemistry of zirconium and hafnium during the last 10 years. It is complementary to the first edition of Encyclopedia of Inorganic Chemistry. The material is presented in two major parts divided in five and three sections respectively. The first part is devoted to syntheses: the first section, by far the largest, covers in a systematic manner bis and mono cyclopentadienyl complexes with +4, +3, and +2 oxidation states and more especially constrained-geometry (CG) complexes, cationic complexes, and anionic or zwitterionic 18-electron complexes; unusual coordination geometries at carbon stabilized by group 4 metallocenes are presented i…

Titanium and zirconium complexes containing the new 2,3-dimethyl-1,4-diphenylcyclopentadienyl ligand. Synthesis, characterization and polymerization behavior

Abstract An easy and inexpensive three-step synthesis of new 2,3-dimethyl-1,4-diphenylcyclopentadiene (3) ligand and the titanium and zirconium homometallocene dichlorides [TiCl2(η5-C5H-2,3-Me2-1,4-Ph2)2] (4), [ZrCl2(η5-C5H-2,3-Me2-1,4-Ph2)2] (5), and the mixed ligand zirconium complex [ZrCl2(η5-C5H-2,3-Me2-1,4-Ph2)(η5-C5H5)] (6) prepared thereof are described. The polymerization of ethene using 4–6/MAO catalysts revealed that zirconocene complexes 5 and 6 displayed moderate and high activity, respectively, whereas the titanium catalyst 4/MAO was inactive. The crystal structures of 4 and 5 were determined by X-ray crystallography.

Inhibition of Cancer Derived Cell Lines Proliferation by Synthesized Hydroxylated Stilbenes and New Ferrocenyl-Stilbene Analogs. Comparison with Resveratrol

Further advances in understanding the mechanism of action of resveratrol and its application require new analogs to identify the structural determinants for the cell proliferation inhibition potency. Therefore, we synthesized new trans-resveratrol derivatives by using the Wittig and Heck methods, thus modifying the hydroxylation and methoxylation patterns of the parent molecule. Moreover, we also synthesized new ferrocenylstilbene analogs by using an original protective group in the Wittig procedure. By performing cell proliferation assays we observed that the resveratrol derivatives show inhibition on the human colorectal tumor SW480 cell line. On the other hand, cell viability/cytotoxicit…

Reactivity of di-n-butyl-dicyclopentadienylzirconium towards amido stabilized stannylenes

Abstract Reaction of Sn[(N(C 6 H 3 i Pr 2 -2,6)(SiMe 3 )] 2 and [{Sn(N(C 6 H 3 i Pr 2 -2,6)(SiMe 3 )(μ-Cl) 2 ] with di- n -butyl-dicyclopentadienylzirconium yielded the trimetallic a carbene-like complex {[(N(C 6 H 3 i Pr 2 -2,6)(SiMe 3 )]( n -Bu)Sn} 2 Cp 2 Zr. The oxidation of {[(N(C 6 H 3 i Pr 2 -2,6)(SiMe 3 )]( n -Bu)Sn} 2 Cp 2 Zr by oxygen gives the five-membered dioxadistannazirconacyclic complex {[(N(C 6 H 3 i Pr 2 -2,6)(SiMe 3 )]( n -Bu)Sn} 2 O 2 Cp 2 Zr.

Formation of arynezirconocenes from substituted diaryl bis (t-butylcyclopentadienyl) zirconium: application to the synthesis of new functionalizedortho-dichalcogenobenzene compounds

The para-substituted diphenylzirconocenes [(t-BuCp)2Zr(p-C6H4R)2; R = Br, NMe2] (A) were easily obtained from the reaction of the appropriate organolithium reagent with bis(t-butylcyclopentadienyl)zirconium dichloride. Elimination of bromobenzene or N,N-dimethylaminobenzene from A by slight heating led to arynezirconocenes into which were inserted two equivalents of elementary chalcogens. As a result dichalcogenated zirconacycles [(t-BuCp)2ZrY2C6H3R; Y = S, Se] (B) were obtained. Complexes B constitute useful potential synthons in organic synthesis and a large family of new functionalized dichalcogenated benzenic compounds was prepared by reacting electrophiles. The structure of complexes B…

Syntheses of polyfunctionalized resveratrol derivatives using Wittig and Heck protocols

Improved protocols for Wittig reaction and palladium-catalyzed Heck coupling give expedient access to a series of unprecedented polyfunctionalized artificial-resveratrol derivatives. In the modified Wittig protocol, trimethylsilyl was used as a highly valuable protective group of the phenolic functions of starting aromatic materials. A clean O-alkylation of hydroxylated stilbenes with ethylene carbonate was also conducted. Thus, Wittig reaction followed by hydroxyethylation take place one-pot with only carbon dioxide as waste. Additionally, a palladium-catalyzed Heck coupling strategy was developed by using ferrocenyl phosphane ligands, and multi-functionalized hydroxylated stilbenes were o…

Diphosphines of dppf-Type Incorporating Electron-Withdrawing Furyl Moieties Substantially Improve the Palladium-Catalysed Amination of Allyl Acetates

Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h - 1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h - 1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of…

Ultra-Low Catalyst Loading as a Concept in Economical and Sustainable Modern Chemistry: The Contribution of Ferrocenylpolyphosphane Ligands

The challenge of sustainability in modern chemistry will be met with new technologies and processes provided significant progress is made in several key research areas, such as the expansion of chemistry from renewable feedstock, the design of environmentally benign chemicals and solvents, the minimization of depletive resources, and the development of high-performance catalysis. In this prospect, ligand chemistry is a pivotal science that links modern-organic,-inorganic, -organometallic, and -coordination chemistry through a vast number of valuable applications, precisely associated to catalysis. We review in this article our recent work on catalysis promoted by original ferrocenyl tetra-,…

Non-degenerate 1,2-silyl shift in silyl substituted alkyltrimethylcyclopentadienes

Abstract The five new silanes C5Me3RSiMenCl3 − n (n = 3, R = i-Pr (5); n = 2, R = i-Pr (6); n = 2, R = s-Bu (7); n = 2, R = cyclohexyl (8); and n = 3, R = t-Bu (9)) were synthesized by reaction of 1-alkyl-2,3,4-trimethylcyclopentadienyl lithium salts with appropriate chlorosilane and characterized by NMR, MS, and IR spectra. At elevated temperatures (250–360 K), all the silanes undergo a non-degenerate sigmatropic silyl rearrangement, which generates non-equivalent structures a and b. The presence of minor structure c was observed in compounds 5 and 7 only. The Diels–Alder cycloaddition of 5 with strong dienophiles tetracyanoethylene (TCNE), and dimethylacetylenedicarboxylate (DMAD) provide…

Ultra‐Low Catalyst Loading as a Concept in Economical and Sustainable Modern Chemistry: The Contribution of Ferrocenylpolyphosphane Ligands (Eur. J. Inorg. Chem. 24/2007)

The cover picture shows an X-ray illustration of the multidentate ferrocenylpolyphosphane 1,1′,2,2′-tetrakis(diphenylphosphanyl)-4,4′-di-tert-butylferrocene. The cisoid conformation of the molecule, evidenced at the solid state, is conserved in solution; the phosphorus arrangement led to a rarely demonstrated multiple-coordination behaviour towards palladium, possibly useful in ultra-low catalyst loading reactions due to an improved stabilization of the metal atom. The multiple phosphane arms and their orientation resemble the elegant and intelligent creature that is the Giant Pacific Octopus (specimen from the Alaska SeaLife Centre in Seward, photo published with the kind permission of Mol…

Group 14 Metalloles, Ionic Species and Coordination Compounds

1 Introduction 2 Synthesis 3 Organic Chemical Properties of Group 14 Metalloles 4 Polymeric Silole-Containing π-Conjugated Systems 5 Ionic Species and Coordination Compounds 6 Addendum 7 Conclusion 8 Acknowledgements Keywords: five-membered heterocyclic dienes; heterocyclopentadienes - heteroles or metalloles; group 14 metalloles, ionic species and coordination compounds; gas-phase pyrolysis of silacyclopent-3-enes; organometallic dihalide reaction with dilithio reagent; group 14 metalloles; HOMO stabilization; polymeric silole-containing pi-conjugated systems

Modular functionalized polyphosphines for supported materials: previously unobserved (31)P-NMR «through-space» ABCD spin systems and heterogeneous palladium-catalysed C-C and C-H arylation.

The modular design of polyphosphines, diversely functionalized for facile immobilization on virtually any kind of support, is reported. Previously unobserved ABCD (31)P NMR spin-spin systems evidence the control exercised on the polyphosphines conformation. We illustrate the catalytic performance at low Pd loading of the recyclable immobilized polyphosphines in C-C bond formation reactions.

Selective formation of a unique diphosphonium-diphosphine from a tetraphosphine double protonation induced by zirconium salts

A mixed ferrocenyl diphosphonium-diphosphine cation, associated with two [ZrCl(5).thf](-) anions, is obtained from a ferrocenyl tetraphosphine, as a unique didentate ionic metalloligand in a perfectly selective reaction induced by ZrCl(4) in THF.

{1,1′-Bis[bis(5-methyl-2-furyl)phosphino]ferrocene-κ2P,P′}dichloroplatinum(II) dichloromethane hemisolvate

The synthesis of the title compound, [FePtCl2(C15H14O2P)2]·0.5CH2Cl2, has been achieved by reacting PtCl2(PhCN)2 with the 1,1′-bis­[bis­(5-methyl-2-furyl)phosphino]ferrocene chelating ligand. The environment at the Pt atom can be described as distorted square-planar, with two cis-Cl atoms and two cis-P atoms.

New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines.

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…

Zirconocen-Benzin-vermittelte intramolekulare Kupplung eines Bis(alkinyl)phosphans, ein Weg zu mono- und tricyclischen 1,2-Dihydrophospheten

ChemInform Abstract: New Concepts in Multidentate Ligand Chemistry: Effects of Multidentarity on Catalytic and Spectroscopic Properties of Ferrocenyl Polyphosphines

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…

Vers une catalyse durable, économe d'atomes et éco-responsable : 0,0001 % de métal, une dose presque homéopathique pour la synthèse pharmaceutique et agrochimique

International audience; Comment mettre la chimie en accord avec un développement sociétal durable, harmonieux et respectueux de l'environnement ? Des chimistes de l'Université de Bourgogne cherchent et trouvent des solutions !

First copper(I) ferrocenyltetraphosphine complexes: possible involvement in Sonogashira cross-coupling reaction ?

Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P′′-[1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Elec…

Isolation, dynamic NMR study and X-ray characterisation of a bis sulfonium zirconocene-ate dimer.

The novel dimer [Cp(2)Zr[upper bond start]([minus sign in circle])S([plus sign in circle])CH(Ph)CH[double bond]C[upper bond end]PPh(2)](2), the first example of a structurally characterised sulfur-bridged binuclear zirconathiolane complex, was prepared, characterised by NMR spectroscopy and X-ray crystallography, and some aspects of its solution behaviour were studied.

Ethene/norbornene copolymerization with (isodicyclopentadienyl)titanium complex-MAO catalyst

Norbornene (NB) homopolymerization and ethene/NB copolymerizations with a silylene-bridged (isodicyclopentadienyl)(tert-butylamido)titanium dichloride-methylalumoxane (MAO) catalyst system were investigated. This catalytic system shows no efficiency towards NB homopolymerization but produces poly(ethene-co-norbornene)s. An increase in the initial NB feed content leads to a loss of copolymerization activity as well as NB copolymer incorporation. The structure of the isodicyclopentadienyl fragment (IsodiCp) has a strong limiting effect on comonomer incorporation possibilities.

CCDC 988195: Experimental Crystal Structure Determination

Related Article: Matthieu Beaupérin, Radomyr Smaliy, Hélène Cattey, Philippe Meunier, Jun Ou, Patrick H. Toy, Jean-Cyrille Hierso|2014|Chem.Commun.|50|9505|doi:10.1039/C4CC04307C

CCDC 988196: Experimental Crystal Structure Determination

Related Article: Matthieu Beaupérin, Radomyr Smaliy, Hélène Cattey, Philippe Meunier, Jun Ou, Patrick H. Toy, Jean-Cyrille Hierso|2014|Chem.Commun.|50|9505|doi:10.1039/C4CC04307C