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PubMed2004

Siloxane-supported organometallic compounds and their catalytic activities for the hydrosilylation of vinylsilanes and dienes.

Two different classes of silicone-modified ligands were prepared: nitrile derivatives, 4'-[3-(organosilyl)propoxy]biphenyl-4-carbonitrile R'3SiC3H6OC6H4C6H4CN (R'3Si- = a: Me3SiOSiMe2-, b: (Me(3)SiO)2SiMe-, c: Me3SiO(Me2SiO)3SiMe2-, d: Me3SiO(Me2SiO)25SiMe2-); and, pyridine derivatives, isonicotinic acid 2-methoxy-4-[3-(organosilyl)propyl]phenyl ester R'3SiC3H6Ph(O)MeOCOC5H4N . Compounds and were bound to Pd and Pt using ligand substitution reactions with organometallic precursors to give (R3SiC3H6OC6H4C6H4CN)2PdCl2, (R3SiC3H6OC6H4C6H4CN)2PtCl2 and (R3SiC3H6C6H3(OMe)OC(O)C5H4N)PtCl2(eta(2)-1-octene). The polydimethylsiloxane (PDMS)-supported Pt and Pd compounds and had excellent solubility in both organic solvents and polysiloxanes. All the Pt compounds exhibited good catalytic activity for hydrosilylation of vinylsilanes. The PDMS-supported Pd compound also was effective catalyst for hydrosilylation of a diene, isoprene, with 1,1,1,3,3-pentamethyldisiloxane MM(H) to produce the 1,4-adduct Me3SiOSiMe2CH2CH=CMeCH2-H as a major product.

Journal Article↗
PubMed2005

Zinc hydrazides and alkoxyhydrazides: organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures.

Tetrameric [{RZn(NHNMe2)}4] (R = Me, Et), the first organometallic zinc hydrazides to be described, have been prepared by alkane elimination from dialkylzinc solutions and N,N-dimethylhydrazine. They were characterised by 1H and 13C NMR and IR spectroscopy, mass spectrometry, elemental analysis and X-ray crystallography. The compounds form asymmetric aggregates containing the novel Zn4N8 core; tetrahedra of Zn atoms bear the alkyl groups at Zn, with the triangular faces bridged by NHNMe2 substituents. The NH groups are connected to two Zn atoms, and the NMe2 groups to one. Hydrolysis of the compounds with water gives [(RZn)4(OH)(NHNMe2)3] as products, which also were characterised as described above. Higher yields of these hydroxo clusters were achieved in one-pot syntheses by reaction of dialkylzinc solutions with mixtures of N,N-dimethylhydrazine and water. They contain Zn4N6O cages, in which one hydroxide in the tetrameric hydrazides described above replaces one NHNMe2 group. Similar products can be prepared with alkoxy instead of hydroxy groups, in analogous one-pot syntheses with alcohols. Alcoholysis of [EtZn(NHNMe2)]4 with methanol or ethanol gave zinc trishydrazide monoalkoxides, [(EtZn)4(OR)(NHNMe2)3] (R = Me, Et), which have constitutions analogous to the monohydroxides. The organozinc bishydrazide bisalkoxides [(MeZn)4(NHNMe2)2(OEt)2] and [(EtZn)4(NHNMe2)2(OEt)2] were obtained in one-pot reactions from dialkylzinc solutions with mixtures of the hydrazine and alcohol, and their crystal structures, confirmed by spectroscopic methods in solution, show an unsymmetrical aggregation with the novel Zn4N4O2 cage structure.

Journal Article↗
PubMed2003

Addition of organometallic compounds to tin-containing cyclic ketones. Remote stereocontrol induced by the stannyl group.

The addition of organometallic reagents to cyclic ketones bearing stannyl groups at an appropriate distance to the carbonyl group occurs with a high level of stereocontrol, giving alcohols resulting from attack of the nucleophile syn to the tin center. This remarkable remote control is a consequence of the anchoring of the organometallic reagent by the tin and carbonyl groups. The degree of selectivity observed depends on the spatial distance between the carbonyl group and the tin center. (Z)-beta-Stannylvinyl ketones (Sn/CO separation: 5 bonds) react with organolithium reagents, showing a high degree of stereocontrol. On the contrary, the analogous ketones with E stereochemistry do not show selectivity at all. In the case of beta-stannyl ketones (Sn/CO separation: 3 bonds), the long distance between the tin center and the carbonyl group does not favor selective addition except when allyllithium derivatives are used. A chelation-controlled pathway assisted by the three-carbon chain of the allyl anion, which compensates the distance between tin and carbonyl groups, has been proposed. The selectivity found for ketones 34-36 (Sn/CO separation: 4 bonds) depends on their structure and varies with the hybridization of the carbon atom linked to the trialkyltin group. Deuterium labeling experiments as well as ab initio molecular-orbital analysis support the mechanistic hypothesis of an intramolecular delivery. Grignard reagents are less selective than organolithium compounds.

Journal Article↗
PubMed2000

New Applications of Polyfunctional Organometallic Compounds in Organic Synthesis Frequently used abbreviations are defined at the end of the article.

In the second half of the twentieth century much effort was invested in the preparation of highly reactive polar organometallic reagents. The high reactivity of these reagents precluded the presence of many functional groups and often good chemoselectivities and stereoselectivities could only by achieved by transmetalation reactions. The synthesis of increasingly complex target molecules and the desire to avoid tedious protection-deprotection steps has led inevitably to the use of functionalized organometallic reagents in retrosynthesis. In the last fifteen years, the generation of organic derivatives of numerous metals and metalloids (Li, Mg, B, Zn, Sn) was investigated. In this review the most important preparations and applications of organometallic reagents in organic synthesis will be covered, with particular emphasis on organozinc reagents.

Journal Article↗
PubMed2004

A new route to chelating bis(aryloxide) ligands and their applications to tantalum and titanium organometallic compounds.

A new route to sterically tuned, chelating bis(aryloxide) ligands is described and demonstrated by the synthesis of 2,2'-ethylenebis(6-isopropylphenol) (1, H(2)BIPP) and transition metal complexes of its dianion. The utility of these ligands in titanium and tantalum organometallic chemistry is shown in the alkylation of (BIPP)TiCl(2) (7) to form (BIPP)TiMe(2) (8) and (BIPP)Ti(CH(2)Ph)(2) (9) and in the alkylation of (BIPP)TaCl(3) (10) and its base adducts to form (BIPP)TaMe(3) (14) and (BIPP)Ta(CH(2)Ph)(3) (13). Structural comparisons of the chelating 2,2'-ethylenebis(6-isopropylphenoxide) (BIPP) ligand with its analogous, nonchelating bis(2,6-dialkylaryloxide) ligand set are examined in the X-ray diffraction studies of (BIPP)TaCl(3)(THF).THF (11.THF) and (BIPP)Ta(CH(2)C(6)H(5))(3) (13).

Journal Article↗
PubMedDate not supplied

Use of the Sonogashira coupling reaction for the "two-step" labeling of phenylalanine peptide side chains with organometallic compounds.

The Pd-catalyzed Sonogashira coupling of ferrocene alkyne derivatives as metal probes to iodophenylalanine containing peptides is described. 4-Iodophenylalanine was incorporated into dipeptides and the neuropeptide [Leu5]-enkephalin (Enk) by solid phase peptide synthesis, thereby creating a functional group suitable for the Sonogashira coupling. The reaction with two different ferrocene alkynes resulted in the corresponding ferrocene-labeled derivatives, which were obtained in good yield and purity. All new compounds were comprehensively characterized, including elemental analysis, 1D and 2D NMR, EI-, FAB- or ESI-MS, IR and UV-vis spectroscopy, and electrochemistry of the ferrocene label. Unlike well-established conjugation methods for peptide side chains such as lysine and cystein, the phenyl group in Phe is not readily available for derivatization. This work presents a versatile procedure for the regioselective introduction of an organometallic label into biologically relevant peptides as exemplified for enkephalin.

Electrochemistry↗
PubMed2004

Are the 11-oxo-steroids really so hindered towards organometallic compounds?

Allylation of an 11-oxo-steroid, the protected adrenosterone, was studied to examine more closely the steric hindrance of such a ketosteroid. While the beta face exhibits, as well known, a strong steric hindrance, the alpha side appears to be only relatively hindered. A high diastereoselectivity was observed in the addition of crotyl magnesium bromide.

Androstenedione↗
PubMed2005

Speciation of organometallic compounds in environmental samples by gas chromatography after flow preconcentration on fullerenes and nanotubes.

The development of a simple speciation method for the determination of lead (trimethyllead(I), dimethyllead(II), triethyllead(I), and diethyllead(II)), mercury (methylmercury(I), ethylmercury(I), mercury(II)), and tin (n-butyltin(III), di-n-butyltin(II), tri-n-butyltin(I), tin(IV)) compounds in environmental samples was described. The potential of C70 fullerenes and multiwalled carbon nanotubes (MWNTs) as sorbents was investigated for the first time; this study revealed that there are no significant differences between them in terms of sensitivity, selectivity, precision, and reusability. Comparative studies showed that MWNTs and C60 and C70 fullerenes were superior to graphitized carbon black and RP-C18 for the extraction of the 11 compounds studied. The accuracy of the MWNT method was evaluated from recovery values with two standard reference coastal sediments, and good concordance in the results were obtained. Detection limits of 0.5-2 pg/mL were obtained when using a sorbent column containing 160 mg of MWNTs (sample breakthrough, 50 mL of water). The method was successfully applied to the determination of lead, mercury, and tin compounds in water and coastal sediment samples with satisfactory results.

Chromatography, Gas↗
PubMed2004

Anionic platinum complexes with 2-pyridylphosphines as ligands for rhodium: synthesis of zwitterionic Pt-Rh organometallic compounds.

Bimetallic zwitterionic platinum(II)-rhodium(I) complexes of the type [(C(6)F(5))(3)Pt(micro-PPy(n)Ph(3)(-)(n)Rh(CO)(2))] and [(C(6)F(5))(3)Pt(micro-PPy(n)Ph(3)(-)(n)())Rh(diene))] (n = 2, 3; Py = 2-pyridyl) have been prepared. The P end of the bridging ligands (micro-PPy(n)Ph(3)(-)(n)) is always coordinated to the Pt center, while the N-donor ends chelate the Rh atom, giving metallacycles comparable to pyrazolylborate-Rh complexes. These metallacycles can adopt two conformations, either with the Pt complex in pseudoaxial position approaching the Rh center or with the Pt complex in a remote position. The preferred conformation depends on the steric hindrance at the rhodium center. In less sterically demanding Rh-carbonyl complexes the Pt moiety gets close to the Rh moiety as this brings closer the opposite charges of the zwitterion. For diene complexes mixtures of conformers are obtained. The X-ray structures of [(C(6)F(5))(3)Pt(micro-PPhPy(2))Rh(COD)] (COD = 1,5-cyclooctadiene) and [(C(6)F(5))(3)Pt(micro-PPhPy(2))Rh(CO)(2)] are reported.

Journal Article↗
PubMed2006

Suzuki coupling at the periphery of diruthenium coordination and organometallic compounds.

A series of diruthenium compounds, Ru2(DArF)3(L")Cl (2), where the auxiliary ligand DArF is DmAniF or D(3,5-Cl2Ph)F and L" is one of the diarylformamidinate ligands containing at least one biphenyl, were prepared from Suzuki reactions between Ru2(DArF)3(L')Cl (1), where L' is (4-I-Ph)NC(H)NPh (N-(4-iodophenyl)-N'-phenylformamidinate) or D(4-I-Ph)F (N,N'-di(4-iodophenyl)formamidinate), and ArB(OH)2 (Ar = Ph and 4-CH3C(O)Ph) in satisfactory yields. Alkynylation of the type 2 compounds with LiCCPh yielded the alkynyl derivatives Ru2(DArF)3(L")(CCPh) (3). Alternatively, type 3 compounds can be prepared from the Suzuki coupling reaction between Ru2(DArF)3(L')(C2Ph) and ArB(OH)2. A structural comparison between the type 1 and 2 compounds revealed minimal changes in the coordination sphere of Ru2 core. Cyclic voltammograms of Suzuki derivatives resemble those of the parent compounds, indicating the retention of the electrophore characteristic of diruthenium species upon peripheral modification.

Journal Article↗
PubMed1996

Reactions of Singlet Oxygen with Organometallic Compounds. 4. Photooxidation of Cationic Iridium(I) and Rhodium(I) Complexes with Weakly Bonded Ligands.

Cationic complexes of the type [M(CO)S(PPh(3))(2)](+) (M = Ir, Rh; S = CH(3)CN) react with singlet oxygen to form the corresponding peroxo complexes [M(CO)S(PPh(3))(2)(O(2))](+). The solvent molecule remains coordinated to the metal in the oxygen adducts. The novel cationic iridium-peroxo complex is stable at room temperature, while the rhodium-peroxo complex is only stable below 0 degrees C. Rate constants for physical and chemical interaction of the complexes with singlet oxygen are somewhat smaller than those for related neutral complexes. Upon addition of alkenes (tetramethylethylene or 1-octene) to the peroxo complexes, neither oxidation of the olefins nor substitution of the acetonitrile ligand was observed. 1-Octene was isomerized to give mostly 2- and 3-octene by the cationic rhodium(I) complex. A cationic iridium complex which already possesses a coordinated diene ligand ([Ir(COD)(PPh(3))(2)](+)) did not react with or quench singlet oxygen.

Journal Article↗