Tungsten Pentacarbonyl Research Articles

Reactions of 1,3,4-triphenyl-1,2-dihydrophosphete

In contrast to previously reported reactivity of the tungsten pentacarbonyl complex of a 2-substituted 1,2-dihydrophosphete, which apparently undergoes electrocyclic ring opening to the corresponding 1-phospha-1,3-butadiene and subsequent [4+2] cycloaddition reactions with dienophiles, the reaction chemistry of 1,3,4-triphenyl-1,2-dihydrophosphete is dominated by its nucleophilic nature. Although low to modest yields of cycloadducts are obtained with some dienophiles, the reactions forming these products are apparently stepwise, as indicated by the loss of stereochemistry in the reaction of dimethyl maleate and in the competitive formation of a phosphorus-free dimer in the reaction of N-methylmaleimide. Dimethyl acetylenedicarboxylate affords three major products, each of which incorporates two equivalents of the acetylene, again apparently a result of initial nucleophilic addition of the dihydrophosphete to the “dienophile.” © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:9–19, 1998

ATTEMPTED SYNTHESIS OF A TRANSITION-METAL STANNAPHOSPHENE COMPLEX

Fluoro-. chloro- and bromostannylphosphines (8–10) complexed on phosphorus by tungsten pentacarbonyl have been synthesized by reaction between lithium mesityl(tungsten pentacarbonyl)phosphide 4, and the corresponding dihalo(diisityl)tin (isityl: 2,4,6-trisopropylphenyl). Reaction of 8, with tert-butyllithium afforded the stable lithium fluorostannylphosphide 11. Addition of Me3SiCl or MgBr2 to 11, gave the corresponding chloro- and bromoderivatives 14, and 15. Similar compounds 16, and 17, were obtained from 9, and 10, and DBU. 11, 15, 16, and 17, present a large 1JSnP coupling constant (2099.0 to 2151.4 Hz) indicating a partial Sn-P double bond.

Ab Initio Calculations of the Geometries and Bonding Energies of Alkane and Fluoroalkane Complexes with Tungsten Pentacarbonyl

Ab initio calculations of the bonding energies of alkanes and fluoromethanes to W(CO)5 have been performed in several basis sets and at a variety of different levels of electron correlation. The Møller−Plesset second-order perturbation (MP2) optimized geometries of the complexes show that a variety of coordination modes are available to alkanes and that the fluoromethanes are coordinated through fluorine. The lowest energy geometry has an η2 agostic bond but two transition states, a second η2 structure and an η3 structure, are close in energy. Although the barriers for exchange of H's at one C are low, the barrier for the exchange of C sites is significantly higher. The MP2 bonding energies have been recalculated with diffuse functions on the metal and with polarization functions on the ligands. Basis set superposition errors (BSSE) have been calculated with every basis set. Even before the BSSE corrections, the MP2 bonding energies are in agreement with the experimental trend within each class of complexes (alkanes and fluoromethanes). These results verify that bonding energies increase with increasing alkane size and that CH3F has the largest bonding energy among fluoroalkane complexes. BSSE corrections play a major role in obtaining good agreement between two classes of complexes because the correction is significantly larger for alkanes in these basis sets. The bonding energy for W(CO)6CH4 has been calculated at different electron correlation levels such as Møller−Plesset third-order (MP3) and fourth-order (MP4) perturbation and quadratic configuration interaction with singles and doubles (QCISD). Excellent agreement with the experimental data was obtained when the MP2 bonding energies in the largest basis set were corrected for BSSE, zero-point energy (ZPE), temperature, and the difference between the MP2 and QCISD energy.

Ab Initio Calculations of the Geometry and Vibrational Frequencies of the Triplet State of Tungsten Pentacarbonyl Amine: A Model for the Unification of the Preresonance Raman and the Time-Resolved Infrared Experiments

Ab initio calculations of the vibrational frequencies of W(CO)5NH3 in its ground electronic 1A1 (b22e4) and lowest excited state 3E (b22e3a11) have been performed at the HF level. The calculated frequencies of the ν(CO) bands are in agreement with observed data on experimentally studied W(CO)5(amine) molecules. The optimized geometries of the ground and the excited states show that the W−N, W−Ceq, W−Cax, C−Oeq bonds lengthen and the C−Oax bond shortens on excitation. Our results resolve an apparent disagreement between the fast time-resolved infrared (TRIR) spectroscopy and the preresonance Raman (PRR) spectroscopy. The unexpected simultaneous lengthening of both W−Ceq and C−Oeq is due to C−Oeq antibonding character in the a1 orbital which more than offsets its loss from the e. In addition a new band, predicted but as yet unresolved in the TRIR, accounts for the C−Oax shortening as expected from the PRR W−Cax lengthening.

Li(dime)2][W(CO)5I] as a novel synthon for the preparation of silyl, amino and organyl derivatives of pentacarbonyl tungsten (dime = diethylene glycol dimethyl ether)

W. Palitzsch, U. Böhme and G. Roewer, Chem. Commun., 1997, 803 DOI: 10.1039/A700215G

Synthesis of New Hybrid Materials by Intercalation of a Bifunctional Aminophosphane and Its Tungsten Pentacarbonyl Complex in α‐Zirconium Phosphate

Functionalization of a phosphane ligand facilitates intercalation of the free ligand and its tungsten pentacarbonyl complex (example shown bottom right) in α-zirconium phosphate (section of structure shown bottom left). Syntheses of intercalated products with the stoichiometry [Zr(HPO4)2(Q)x·yH2O] (Q = Ph2PCH2CH2NMe2, x = 0.46, y = 1.1; Q = (OC)5W(Ph2PCH2CH2NMe2), x = 0.51, y = 1.5) are reported.

Di- and triphospha-ferrocenes: crystal and molecular structures of [Fe(η 5-C 5Me 5) (η 5-C 3tBu 3P 2)] and of the adducts [Fe(η 5-C 5Me 5) (η 5-C 2tBu 2P 3) Mo(CO) 5] and [Fe(η 5-C 5Me 5 (η 5-C 2tBu 2P 3)W(CO) 5] 1

Synthesis and structural studies of the iron “sandwich” complex [Fe( η 5-C 5Me 5( η-C 3 t Bu 3P 2)] 1 are described. The lone pair electrons of the two adjacent phosphorus atoms of the C 2 tBu 2P 3 ring in the triphospha-ferrocene complex [Fe( η 5-C 5Me 5)( η 5-C 2 t Bu 2P 3)] 2 can ligate to other metal centres. The results of single crystal X-ray structural studies of the molybdenum and tungsten pentacarbonyl η 1-complexes [Fe( η 5-C 5Me 5)( η 5-C 2 t Bu 2P 3)M(CO) 5] ( 4: M = Mo, 5: M = W) are discussed; they form an isostructural series with the previously reported chromium complex. The starting material 2 reacts with [(C 5H 4Me)(CO) 2Mn(THF)] to form the adduct [Fe( η 5-C 5Me 5)( η 5-C 2 t Bu 2P 3)Mn(CO) 2( η 5-C 5H H 4Me) ] 6. The phenyl-substituted di- and triphosphacyclopentadienides [Na(DME) 3][C 3Ph 3P 2] and [Na(DME) 3][C 2Ph 2P 3] (DME = 1,2-dimethoxyethane) react with ferrous chloride and Li[C 5Me 5] to give the ‘sandwich’ compounds [Fe( η 5-C 5Me 5)( η 5-C 3Ph 3P 2)] 9 and [Fe( η 5-C 5-C 5Me 5( η 5-C 2Ph 2P 3)] 10. The The latter reacts with W(CO) 5(THF) to yield the η 1-complex [Fe( η 5- C 5Me 5)( η 5-C 2Ph 2P 3)W(CO) 5] 11.

ChemInform Abstract: Tungsten Pentacarbonyl as a Potential Protecting Group for Soft Lewis Base Centres in Alkylation of Multifunctional Molecules.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The selective complexation of adamantane nitriles by tungsten pentacarbonyl

Adamantyl-1,3,4-oxathiazol-2-one is usually prepared as a mixture with 1-adamantanecarbonitrile. To separate these two compounds the mixture is reacted with thf•W(CO)5, which selectively forms a complex with the nitrile. The resulting mixture can then be readily separated into pure compounds by sublimation. Characterization data are presented, including the X-ray crystal structure of the nitrile complex, which can be prepared directly from the reaction of the adamantyl nitrile and thf•W(CO)5. (Crystal data for C16H15NO5W: orthorhombic, space group Pmcn, a = 10.5869(19) Å, b = 14.0622(22) Å, c = 23.342(4) Å, V = 3475.0(11) Å, Z = 8, R = 0.042.) The nitrile can be recovered from the complex by reaction with P(C6H5)3 followed with separation by sublimation. The reaction of the related 1-cyano-3-(1,3,4-oxathiazol-2-on-5-yl)-adamantane with thf•W(CO)5 yields a complex in which the site of coordination is shown spectroscopically to be the nitrile moiety. Semi-empirical calculations at the PM3 level indicate that the oxathiazolone heterocycle may be a poor ligand due to the influence of the exo- and endo-cyclic oxygen atoms. Key words: oxathiazolone, nitrile, tungsten, complexation, selectivity, adamantane.not available

A New Stereoselective Synthesis of Phosphiranes.

The synthesis of phosphiranes from primary phosphines and diol ditosylates was found to be stereoselective, and chiral phosphiranes were prepared from optically pure diols. The four optical isomers of 1-mesityl-2,3-dimethylphosphirane, (2S,3S)-(+)-3, (2R,3R)-(-)-4, anti-cis-(meso)-5, and syn-cis-(meso)-6, were all synthesized from mesitylphosphine and the corresponding diol ditosylates. Compound 6 was unstable, but compounds 3, 4, and 5 were all isolated in pure form. Their structure assignments were based on the NMR coupling constants J(P-H) and J(P-C). The phosphiranes were transformed into tungsten pentacarbonyl complexes. Tungsten tetracarbonyl-triphenylphosphine complexes (22, 23, 24) of compounds 3, 4, and 5 were synthesized in high yields by the reaction of the phosphiranes and W(CO)(4)(PPh(3))(THF). The absolute stereochemistry of the phosphiranes 3, 4, and 5 was determined by X-ray crystal structure analysis of compounds 22, 23, and 24. Stereochemical effects on NMR coupling constants and mass spectra of the phosphiranes are discussed.

Tungsten pentacarbonyl as a potential protecting group for soft lewis base centres in alkylation of multifunctional molecules

Reaction of W(CO) 6 or (PhNH 2)W(CO) 5 with the molecules which possess both diphenylphosphanyl- and dialkylamino group or nitrogen — containing hetcrocyclic ring proceeds selectively through “soft” Lewis base groups and can be used for the protection of the groups from alkylalion. As a rule, the diphenylphosphanyl group participates in the co-ordination, but in some cases an sp 2-hybridized nitrogen was shown to be the preferable co-ordination site. The new synthesized compounds have been characterized by NMR, IR spcctroscopy, and elemental analysis.

ChemInform Abstract: Chromium and Tungsten Pentacarbonyl Groups as Reactivity and Selectivity Auxiliaries in (3 + 2) Cycloaddition of Alkynyl Fischer Carbene Complexes with N‐Alkyl Nitrones.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The photochemical behaviour of matrix-isolated W(CO) 6 in the presence of alkynes

The outcome of UV photolysis of W(CO) 6 molecules isolated in a solid CH 4 or Ar matrix in the presence of an alkyne RCCR′ (R,R′H,H; Me,H; or Me, Me) at ca. 20 K has been monitored by recording the IR and UV-vis absorption spectra of the deposit. The results indicate that irradiation with light having wavelengths near 313 nm results in the formation of the ( η 2-alkyne)tungsten pentacarbonyl complex, [( η 2-RCCR′)W(CO) 5], in addition to [X … W(CO) 5] (X  CH 4 or Ar), and free CO. In the case of a terminal alkyne, e.g. HCCH or MeCCH, however, photolysis under these conditions gives, in addition to the η 2-alkyne complex and in significantly greater yield, what appears to be the vinylidene derivative [R(H)CCW(CO) 5] (RH or Me). Prolonged irradiation with UV light ( λ = ca. 313 or 369 nm) causes the various pentacarbonyl complexes to lose CO with the formation of tetracarbonyl species; prominent among the products issuing from the W(CO) 5/C 2H 2 system are [( η 2-HCCH)( η 1-H 2CC)W(CO) 4] (in C 2H 2-rich matrices) and [( η 2-HCCH)W(CO) 4] in which the alkyne is acting formally as a 4e ligand. The results are significant in relation to the likely intermediate stages in the photocatalytic polymerization of terminal alkynes induced by tungsten hexacarbonyl.

Chromium and Tungsten Pentacarbonyl Groups as Reactivity and Selectivity Auxiliaries in [3 + 2] Cycloaddition of Alkynyl Fischer Carbene Complexes with N-Alkyl Nitrones

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChromium and Tungsten Pentacarbonyl Groups as Reactivity and Selectivity Auxiliaries in [3 + 2] Cycloaddition of Alkynyl Fischer Carbene Complexes with N-Alkyl NitronesKin Shing Chan, Ming Lok Yeung, Wai-kin Chan, Ru-Ji Wang, and Thomas C. W. MakCite this: J. Org. Chem. 1995, 60, 6, 1741–1747Publication Date (Print):March 1, 1995Publication History Published online1 May 2002Published inissue 1 March 1995https://doi.org/10.1021/jo00111a036RIGHTS & PERMISSIONSArticle Views944Altmetric-Citations65LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (903 KB) Get e-Alerts Get e-Alerts

Regiospezifische Insertion von [SCN]- und [SeCN]- in die S – C- bzw. Se– C-Bindung Übergangsmetall-koordinierter Thietane und Selenetane<br />Regiospecific Insertion of [SCN]- and [SeCN]- in the S–C- and Se–C-Bond of Transition-Metal-Coordinated Thietanes and Selenetanes

Pentacarbonyl(thietane)tungsten complexes react with thiocyanate, [SCN]-, and SiO2/H2O by insertion of the CN group into a S—C bond of the four-membered heterocycle, 1,3-migration of the pentacarbonyltungsten fragment and protonation of the nitrogen atom to give tungsten-coordinated thiazinthione complexes. Analogously, the reactions of a thietane tungsten complex with [SeCN]- and SiO2/H2O affords a thiazinselone complex. A selenazinthione complex is obtained from a selenetane complex and [SCN]- (+ SiO2/H2O). The insertions are regiospecific and stereoselective. The structure of the trans-isomer of a pentacarbonyl-(thiazinthione) complex has been established by X-ray structure analysis.

Synthesis and reactivity of tungsten pentacarbonyl hydroxo and bicarbonato complexes. Molecular structure of [PPN][W(CO)5HCO3], an organometallic analog for carbonic anhydrase

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and reactivity of tungsten pentacarbonyl hydroxo and bicarbonato complexes. Molecular structure of [PPN][W(CO)5HCO3], an organometallic analog for carbonic anhydraseDonald J. Darensbourg, Monica L. Meckfessel Jones, and Joseph H. ReibenspiesCite this: Inorg. Chem. 1993, 32, 22, 4675–4676Publication Date (Print):October 1, 1993Publication History Published online1 May 2002Published inissue 1 October 1993https://doi.org/10.1021/ic00074a003RIGHTS & PERMISSIONSArticle Views177Altmetric-Citations18LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (278 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Access to New Phosphorus Structures by the Way of the Transient Terminal Phosphinidene Complexes

Abstract The Tungstaphosphirenes, Phosphaalkenes, Phosphahexatrienes, η4-phosphabutadiene complexes and 1,2-dihydrophosphete ring have been synthesized by coupling reactions of carbyne or carbene complexes with the transient phenyl phosphinidene pentacarbonyl tungsten [PhP[dbnd]W(CO) 5]. The preparation of other heterocycles such as Dihydrodiphosphetes and Dihydrophosphepines has been realized from the vinylphosphinidene complexes via a 4π-electrocyclization and a Phospha-Cope rearrangement respectively.

Structural and reactivity studies of a cyanoacetic acid derivative of tungsten pentacarbonyl. X-ray structure of W(CO)5NCCH2COOH

The new cyanoacetic acid complex W(CO) 5 NCCH 2 COOH (1) has been synthesized from the reaction of W(CO) 5 THF and NCCH 2 COOH. The molecular structure of 1 has been determined by X-ray diffraction methods. The compound crystallizes in the triclinic space group P1.

Pressure acceleration of [2 + 2] cycloaddition reactions on the coordinated ligand of chromium and tungsten pentacarbonyl carbene complexes

Pressure acceleration of [2 + 2] cycloaddition reactions on the coordinated ligand of chromium and tungsten pentacarbonyl carbene complexes

Thietane and selenetane complexes by thermal cycloaddition of vinyl ethers to transition metal coordinated thio- and seleno-aldehydes

Pentacarbonyl tungsten coordinated thio- and seleno-benzaldehydes react with vinyl ethers by regiospecific addition of the CC to the XC bond of the heteroaldehydes to form thietane and selenetane complexes, respectively.