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Annual survey of organometallic metal cluster chemistry for the year 2000

The synthetic, mechanistic, and structural chemistry of organometallic metal cluster compounds is reviewed for the year 2000.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Non-classical hydrosilane mediated reductions promoted by transition metal complexes

This article reviews the most recent advances on the study of non-classical mechanisms for the reduction of organic substrates with hydrosilanes catalyzed by transition metals. A wide variety of catalytic cycles that go beyond the classical steps described for Ojima, Chalk-Harrod and modified Chalk-Harrod mechanisms, as representative examples, have been proposed in recent years. In this review, these alternative mechanistic proposals have been analyzed and classified according to the type of substrate, focusing on the reduction/hydrosilylation of carbonyl compounds (ketones and aldehydes), carbon dioxide, silylesters, amides, N-heterocycles, alkyl halides, nitriles, alkenes and alkynes. In spite of the broad diversity of non-classical reaction mechanisms hitherto reported, the catalytic cycles described for each substrate have been arranged in different categories according to their characteristics. The epigraph dedicated to the first type of substrate (carbonyl compounds) comprises most of the mechanisms described in this review for the reduction of polar bonds, which, to some extent, show a relationship to those proposed for non-polar bonds (alkenes and alkynes). Remarkable types of reaction mechanisms that will be dealt with in this work are: ionic mechanisms, ligand-assisted mechanisms, nonhydride mechanisms, NHC-Cu-H mediated mechanisms, and silylene-mediated mechanisms.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis of Ni(II) Complexes Supported by Tetradentate Mixed-Donor Bis(amido)/Phosphine/Phosphido Ligands by Phosphine Substituent Elimination

A convenient nickel-templated phenyl elimination route is described for the synthesis of phosphide-containing multidentate ligands from triarylphosphine precursors. Treating Ni(COD)2 with the neutral bis(amine)/bis(phosphine) ligand precursor H2 4Ph[PNNP] affords bis(amido)/bis(phosphine) complex 1. Treatment of 1 with 1 equiv of KH leads to elimination of a phenyl group from one of the phosphine fragments, generating bis(amido)/phosphine/phosphido complex 3Ph[PNNP]Ni- (2). Alternatively, excess KH or nBuLi affords the bis(amido)/bis(phosphide) complex 2Ph[PNNP]Ni2- (3 or 4, respectively) by elimination of two phenyl substituents. These reactions are high-yielding and provide a unique and straightforward route to chelating phosphido ligands that would otherwise be challenging to synthesize.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

Some scientific research about 4020-99-9

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Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, 4020-99-9, the author is Fernandez-Garcia and a compound is mentioned, 4020-99-9, Methoxydiphenylphosphine, introducing its new discovery.

Reactions of [1,2-bis(diphenylphosphinite)ethane]bromotricarbonylrhenium(I) with phosphites, phosphonites and phosphinites. The crystal structure of [ReBr(CO)2{Ph2PO(CH2)2 OPPh2}L?] [L? = P(OCH3)3, P(OC2H5)3 and PPh(OC2H5)2]

The rhenium carbonyl complexes cis,mer-[ReBr(CO)2(L)(L?)] [L = 1,2-bis(diphenylphosphinite)ethane, L? = P(OMe)3 (1), P(OEt)3 (2), PPh(OMe)2 (3), PPh(OEt)2 (4), PPh2(OMe) (5), PPh2(OEt) (6)] were synthesised by reaction of [ReBr(CO)3L] with 1 equiv. of the appropriate phosphite, phosphonite or phosphinite. The coordination geometry has been established by NMR, IR and, for compounds 1, 2 and 4, X-ray crystallography. These compounds consist of slightly distorted octahedral monomers. The conformation of the seven-membered ReP2O2C2 chelate ring is a twist-chair for compound 1 and a twist-boat for compounds 2 and 4.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Spin-Selective Photoreduction of a Stable Radical within a Covalent Donor-Acceptor-Radical Triad

Controlling spin-spin interactions in multispin molecular assemblies is important for developing new approaches to quantum information processing. In this work, a covalent electron donor-acceptor-radical triad is used to probe spin-selective reduction of the stable radical to its diamagnetic anion. The molecule consists of a perylene electron donor chromophore (D) bound to a pyromellitimide acceptor (A), which is, in turn, linked to a stable alpha,gamma-bisdiphenylene-beta-phenylallyl radical (R?) to produce D-A-R?. Selective photoexcitation of D within D-A-R? results in ultrafast electron transfer to form the D+?-A-?-R? triradical, where D+?-A-? is a singlet spin-correlated radical pair (SCRP), in which both SCRP spins are uncorrelated relative to the R? spin. Subsequent ultrafast electron transfer within the triradical forms D+?-A-R-, but its yield is controlled by spin statistics of the uncorrelated A-?-R? radical pair, where the initial charge separation yields a 3:1 statistical mixture of D+?-3(A-?-R?) and D+?-1(A-?-R?), and subsequent reduction of R? only occurs in D+?-1(A-?-R?). These findings inform the design of multispin systems to transfer spin coherence between molecules targeting quantum information processing using the agency of SCRPs.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis and 13C NMR study of the triangulo-clusters [Pt3(mu-CO)3 – (n)(mu-SO2)(n)(PR3)3] (n = 0-3)

[Pt3(mu-CO)3(PPh3)3] was prepared in high yield by the reaction of [Pt3(mu-CO)3(PPh3)4] with H2O2. The carbonyl ligands in [Pt3(mu-CO)3(PR3)3] (PR3 = PPh3, PPh2Bz, PCy3, P(i)Pr3) may be completely replaced by sulfur dioxide to give [Pt3(mu-SO2)3(PR3)3] or partially by one SO2 to give [Pt3(mu-CO)2(mu-SO2)(PR3)3] (PR3 = PCy3 and P(i)Pr3). On the other hand, the addition of one molar equivalent of carbon monoxide to [Pt3(mu-SO2)3(PR3)3] (PR3 = PCy3; P(i)Pr3) gave the complexes [Pt3(mu-CO)(mu-SO2)2(PR3)3]. Complete simulation of the 13C NMR spectra could be achieved with the help of 195Pt NMR data. (C) 2000 Elsevier Science S.A.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, the author is Doorn, Johannes A. van and a compound is mentioned, 84127-04-8, Bis(4-methoxyphenyl)phosphine, introducing its new discovery. 84127-04-8

Reductive cleavage of the carbon-phosphorus bond with alkali metals. III Reactions of arylalkylphosphines

The reductive cleavage of phenylalkylphosphines Ph2PR, PhPR2 (R = Bu, iPr) with Na/NH3 is unselective; both phenyl and alkyl groups can be cleavaged and Birch reduction may occur.Reaction of Ph2tBuP gives a high yield of diphenylphosphide.Polar groups (CO2Na, SO3Na) at the omega position of primary alkyl groups may lead to an increase in selectivity; Birch reduction is suppressed and a functionalised secondary phosphide is obtained.From diarylbenzyl- and diarylallylphosphines, the benzyl and allyl groups are selectively removed; Ar2PH and ArRPH are formed in high yield after hydrolytic work-up unless the aryl group bears F, CF3 or (CH3)2N substituents.From the reaction mixture of Ph2PCH2Ph we have isolated 1,2-diphenylethane. 2-Methoxyphenyl and 2,6-dimethoxyphenyl groups are selectively removed from Ar2BuP, ArPhBuP and Ar2P(CH2)3PAr2, forming ArBuPH, PhBuPH and ArP(H)(CH2)3(H)PAr, respectively.A double-cleavage reaction of Ar2RP may occur in low yield. 2,6-(dimethoxyphenyl-dibutylphosphine gives dibutylphosphine in moderate yield.When compounds with a 2,6-dimethoxyphenyl moiety are allowed to react with Li/THF, removal of a methyl group leads to novel phosphinophenols.It is concluded that cleavage of alkyl groups R selectively occurs when R radical is relatively stable (tBu, PhCH2> iPr > Bu).

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Rapid phosphorus(III) ligand evaluation utilising potassium selenocyanate

Oxidative addition of SeCN- to tertiary phosphine ligands has been investigated in methanol at 298 K by use of UV-Vis stopped-flow and conventional spectrophotometry. In most cases kobsvs. [SeCN -] plots were linear with zero intercepts corresponding to a rate expression of kobs = k1[SeCN-]. Reactions rates are dependent on the electron density of the phosphorus centre with k 1 varying by five orders of magnitude from 1.34 ¡À 0.02 ¡Á 10-3 to 51 ¡À 3 mol-1 dm3 s-1 for P(2-OMe-C6H4)3 to PCy3 respectively. Activation parameters range from 27 ¡À 1 to 49.0 ¡À 1.3 kJ mol-1 for DeltaH? and -112 ¡À 9 to -140 ¡À 3 J K-1 mol-1 for DeltaS ? supporting a SN2 mechanism in which the initial nucleophilic attack of P on Se is rate determining. Reaction rates are promoted by more polar solvents supporting the mechanistic assignment. Reasonable linear correlations were observed between log k1vs. pKa, 1JP-Se and chid values of the phosphines. The reaction rates are remarkably sensitive to the steric bulk of the substituents, and substitution of phenyl rings in the 2 position resulted in a decrease in the reaction rate. The crystal structures of SePPh2Cy and SePPhCy2 have been determined displaying Se-P bond distances of 2.111(2) and 2.1260(8) respectively. The Royal Society of Chemistry 2008.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, the author is Das, Sanjib and a compound is mentioned, 131274-22-1, Tri-tert-butylphosphonium tetrafluoroborate, introducing its new discovery. 131274-22-1

Design, synthesis and pharmacological evaluation of novel polycyclic heteroarene ethers as PDE10A inhibitors: Part II

We report the design and synthesis of novel pyrrolo[3,2-b]quinoline containing heteroarene ethers as PDE10A inhibitors with good to excellent potency, selectivity and metabolic stability. Further optimization of this primary series resulted in the identification of 1-methyl-3-(4-{[3-(pyridine-4- yl)pyrazin-2-yl]oxy}phenyl)-1H-pyrrolo[3,2-b]pyridine 13a with good hPDE10A potency (IC50: 6.3 nM), excellent selectivity over other related PDEs and desirable physicochemical properties. The compound exhibited high peripheral and adequate brain levels upon oral dosing in rodents. The compound also showed excellent efficacy in multiple preclinical animal models related to psychiatric disorders, particularly schizophrenia.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A novel convenient synthesis of aryl phosphines containing reactive functional groups

A convenient method is described for the preparation of Ph2PC6H4COOH-2 (2) and Ph2PC6H4CHO-2 (5).

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate