Diphosphine Derivatives Research Articles

Palladium Catalysts Supported in Microporous Phosphine Polymer Networks.

A new set of microporous organic polymers (POPs) containing diphosphine derivatives synthesized by knitting via Friedel-Crafts has been attained. These amorphous three-dimensional materials have been prepared by utilizing diphosphines, 1,3,5-triphenylbenzene, and biphenyl as nucleophile aromatic groups, dimethoxymethane as the electrophilic linker, and FeCl3 as a promoting catalyst. These polymer networks display moderate thermal stability and high microporosity, boasting BET surface areas above 760 m2/g. They are capable of coordinating with palladium acetate, using the phosphine derivative as an anchoring center, and have proven to be highly efficient catalysts in Suzuki-Miyaura coupling reactions involving bromo- and chloroarenes under environmentally friendly (using water and ethanol as solvents) and aerobic conditions. These supported catalysts have achieved excellent turnover numbers (TON) and turnover frequencies (TOF), while maintaining good recyclability without significant loss of activity or Pd leaching after five consecutive reaction cycles.

Electrocatalytic proton-reduction behaviour of telluride-capped triiron clusters: tuning of overpotentials and stabilization of redox states relative to lighter chalcogenide analogues.

Reaction of [Fe3(CO)9(μ3-Te)2] (1) with the corresponding phosphine has been used to prepare the phosphine-substituted tellurium-capped triiron clusters [Fe3(CO)9(μ3-Te)2(PPh3)] (2), [Fe3(CO)8(μ3-Te)2(PPh3)] (3) and [Fe3(CO)7(μ3-Te)2(μ-R2PXPR2)] (X = CH2, R = Ph (4), Cy (5); X = NPri, R = Ph (6)). The directly related cluster [Fe3(CO)7(μ3-CO)(μ3-Te)(μ-dppm)] (7) was isolated from the reaction of [Fe3(CO)10(μ-Ph2PCH2PPh2)] with elemental tellurium. The electrochemistry of these new clusters has been probed by cyclic voltammetry, and selected complexes have been tested as proton reduction catalysts. Each 50-electron dicapped cluster exhibits two reductive processes; the first has good chemical reversibility in all cases but the reversibility of the second is dependent upon the nature of the supporting ligands. For the parent cluster 1 and the diphosphine derivatives 4-5 this second reduction is reversible, but for the PPh3 complex 3 it is irreversible, possibly as a result of CO or phosphine loss. The nature of the reduced products of 1 has been probed by DFT calculations. Upon addition of one electron, an elongation of one of the Fe-Te bonding interactions is found, while the addition of the second electron affords an open-shell triplet which is more stable by 8.8 kcal mol-1 than the closed-shell singlet dianion and has two elongated Fe-Te bonds. The phosphine-substituted clusters also exhibit oxidation chemistry but with poor reversibility in all cases. Since the reduction potentials for the tellurium-capped clusters occur at more positive potentials than for the sulfur and selenium analogues, and the redox processes also show better reversibility than for the S/Se analogues, the tellurium-capped clusters 1 and 3-5 have been examined as proton reduction catalysts. In the presence of p-toluenesulfonic acid (TsOH) or trifluoroacetic acid (TFA), these clusters reduce protons to H2 at both their first and second reduction potentials. Electron uptake at the second reduction potential is far greater than the first, suggesting that the open-shell triplet dianions are efficient catalysts. As expected, the catalytic overpotential increases upon successive phosphine substitution but so does the current response. A mechanistic scheme that takes the roles of the supporting ligands on the preferred route(s) to H2 production and release into account is presented.

Ruthenium [NNN] and [NCN]-type pincer complexes with phosphine coligands: synthesis, structures and catalytic applications

A series of ruthenium [NNN]- or [NCN]-type complexes (3–7) bearing PPh3 ancillary ligands have been synthesized from pyridine- or phenylene-bridged bis(triazoles) 1 and 2. In the case of [NNN]-pincer complex 3, an unusual and unexpected cis-orientation adopted by two sterically demanding PPh3 ligands was observed, and such configuration proved to be unchanged in solution for a long time. By contrast and as expected, the two phosphines are found to be trans to each other in the case of [NCN]-type pincer complex 4, but an oxidation of RuII center to RuIII occurred. Complex cis-3 underwent ligand exchanges leading to the formations of diphosphine derivatives 5 and 6. As a representative, cis-3 was treated with the base in isopropanol affording a mixture of Ru–hydrido complexes with various phosphine binding modes, one of which (trans-7) bearing two trans-standing phosphines has been successfully isolated and fully characterized. The catalytic performances of all newly synthesized Ru complexes have been examined and compared in transfer hydrogenations of ketones and enones, in which mono-phosphine complexes proved to be significantly superior to their diphosphine counterparts. The catalytic process proved to involve Ru–H key intermediates, but the trans-oriented Ru–H species is unlikely to be the main catalytic contributor. In particular, the best performer cis-3 exhibits high chemoselectivity in certain cases catalyzing α,β-unsaturated ketones, whose behavior is quite different compared to most precedents.

Applications of Diphosphines in Radical Reactions

AbstractRecently, the importance of organophosphorus compounds in organic chemistry has increased. Diphosphines are an attractive source of phosphorus containing two phosphorus groups, which can theoretically be introduced into a carbon framework with high atom economy. There are several diphosphine derivatives, which are closely related to diphosphines, but their reactivities are completely different. In this Minireview, we describe various phosphination reactions with diphosphines and their derivatives under radical conditions.

OsXCl(phosphine)2(diamine) and OsXCl(diphosphine)(diamine) (X = Cl, H) Complexes for Ketone Hydrogenation

The osmium complex trans-[OsCl2(PPh3)2(en)] (2) was prepared by reaction of [OsCl2(PPh3)3] (1a) with ethylenediamine (en), whereas the diphosphine derivatives trans-[OsCl2(dppf)(NN)] (NN = en (3), bn (4; bn = 1,4-butanediamine)) and trans-[OsCl2(dpbp)(en)] (5) were obtained from 1a, dppf or dpbp, and the corresponding NN ligand in CH2Cl2 or toluene. An X-ray diffraction study has been provided for 3. The isolation of the chiral derivatives trans-[OsCl2(diphosphine)((R,R)-dpen)] (diphosphine = dppf (6), dpbp (7), (R,R)-skewphos (8)) was achieved by reacting 1a with the diphosphine and (R,R)-dpen in toluene. Treatment of the precursor [Os2Cl4(P(m-tolyl)3)5] (1b) with en afforded [OsCl2(P(m-tolyl)3)2(en)] (9), while reaction of 1b with dppb and N,N-dmen gave [OsCl2(dppb)(N,N-dmen)] (10). The chiral derivatives [OsCl2(diphosphine)(NN)] (11–21; diphosphine = (S)-MeObiphep, (R)-MeObiphep, (R)-xylMeObiphep, (R)-binap, (S)-xylbinap, (R)-xylbinap, (R,S)-Josiphos*; NN = en, (R,R)-dpen, (R)-daipen, (R,R)-dppn) were ...

Chiral diphosphine derivatives of alkylidyne tricobalt carbonyl clusters – A comparative study of different cobalt carbonyl (pre)catalysts for (asymmetric) intermolecular Pauson–Khand reactions

Reaction of the tricobalt carbyne cluster [Co3(μ3-CH)(CO)9] with chiral diphosphines of the Josiphos and Walphos families affords the new clusters [Co3(μ3-CH)(CO)7(P–P∗)] in good yield (P–P∗=J004 (1), J005 (2), J007 (3), W001 (4), W003 (5)). The new alkylidyne tricobalt clusters, and the previously known [Co3(μ3-CH)(CO)7(μ-J003)], have been tested as catalysts/catalyst precursors for intermolecular Pauson–Khand cyclization, using norbornene and phenylacetylene as substrate. The diphosphine-substituted tricobalt carbonyl clusters proved to be viable catalysts/catalyst precursors that gave products in moderate to good yields, but the enantiomeric excesses were low. When the chiral diphosphine ligands were used as promoters/auxiliary ligands for the same Pauson–Khand reaction, using either [Co2(CO)8] or [Co4(CO)12] as catalyst precursors, both the overall yields and the selectivities with respect to cyclopentenone formation were significantly improved. The best results were obtained for ligands J007 and W001, with [Co4(CO)12] as pre-catalyst, where yields of 96%, and virtually 100% selectivity were obtained. However, the enantioselectivity of product formation was low or non-existent. The crystal structure of [Co3(μ3-CH)(CO)7(μ-J004)] is described. [J003=[(R)-1-{(S)-2-(dicyclohexylphosphino)-ferrocenyl} ethyldicyclohexylphosphine], J004=[(R)-1-{(S)-2-(dicyclohexylphosphino)-ferrocenyl} ethyldiphenylphosphine], J005=[(R)-1-{(S)-2-(diphenylphosphino)ferrocenyl}ethyl-di-3,5-xylylphosphine], J007=[(R)-1-{(S)-2-di-(4-methoxy-3,5-dimethylphenyl)phosphino)ferrocenyl} ethyldicyclohexylphosphine], W001=[(R)-1-{(R)-2-(2′-diphenyl phosphinophenyl)ferrocenyl} ethyldi(bis-3,5-trifluoromethylphenyl)phosphine], W003 [(R)-1-{(R)-2-(2′-diphenylphosphino-phenyl)ferrocenyl}ethyldi(3,5-xylyl)phosphine].

Diphosphines and pyrazole/pyrazolate-type ligands as building blocks in luminescent Au(I) complexes

A series of gold(I) complexes containing diphenylphosphine bridging ligands, dppm, dppe, dpephos, dbfphos and biphep and co-ligands of the type pyrazole have been synthesized. The X-ray crystal structures of [Au 2(μ-dpephos)(μ-pz 2CH3)][PF 6], [Au 2(μ-dbfphos)(μ-pz 2CH3)][PF 6], and of the starting compound [Au 2Cl 2(μ-biphep)] indicate that the structural and stoichiometric characteristics of the new complexes depend on the diphosphine ligand. The three complexes show Au⋯Au contacts between 3.27 Å and 3.30 Å, with that of the biphep compound being the shortest. Digold (I)-diphosphine derivatives with a bridging pyrazolate ligand are obtained in all cases, except when [Au 2Cl 2(μ-biphep)] is used as starting material. Surprisingly, in this case, two monodentate neutral pyrazole ligands are attached to the gold atoms. The new complexes are luminescent in the solid state at 77 K and in solution both at room temperature and 77 K. Low energy emission bands related to the presence of Au⋯Au interactions have been identified in some of the compounds in the solid state and/or in solution.

Synthesis, reactivity investigation, and X-ray diffraction structures of new platinum(II) compounds containing redox-active diphosphine ligands

Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl 2(cod) ( 1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl 2(bpcd) ( 2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl 2(abpcd) ( 3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na 2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) ( 4). Compounds 2– 4 have been fully characterized in solution by IR and NMR spectroscopies ( 1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2– 4 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in these systems has been established by MO calculations at the extended Hückel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives.

Mononuclear, Dinuclear, and Hexanuclear Gold(I) Complexes with (aza-15-crown-5)Dithiocarbamate

The reactions of sodium (aza-15-crown-5)dithiocarbamate with [AuClL] precursors lead to mono-, di-, or hexanuclear derivatives depending on L. The homoleptic hexanuclear gold(I) cluster [Au6(S2CNC10H20O4)6] is formed by displacement of the chloride and isocyanide ligands in [AuCl(CN(2,6-Me2C6H3))]. X-ray diffraction studies show a novel geometry in gold cluster chemistry where the six gold atoms display a cyclohexane-like geometry in a chair conformation with Au-Au-Au angles of 117.028(9) degrees, two short gold-gold distances of 2.9289(5) A, and bidentate bridging dithiocarbamate ligands. The molecular structure shows a crown of gold atoms surrounded by crown ethers. This derivative luminesces at 569 nm at room temperature in the solid state. A dinuclear isomer [Au2(S2CNC10H20O4)2] had been reported previously and was obtained by reaction with [AuCl(SMe2)]. The mechanism to obtain the hexanuclear derivative involves a mononuclear intermediate [Au(S2CNC10H20O4)(CNR)] for which the X-ray structure shows a short gold-gold distance of 3.565 A with the two molecules in an anti configuration. Phosphine gold(I) mononuclear derivatives [Au(S2CNC10H20O4)(PR3)] (R = Me, Ph, both characterized by X-ray diffraction) and dinuclear diphosphine derivatives [{Au(S2CNC10H20O4)}2(mu-P-P)] (P-P = dppm, bis(diphenylphosphinomethane); dppp, 1,3-bis(diphenylphosphinopropane); and dppf, 1,1'-bis(diphenylphosphinoferrocene)) are also reported. In the mononuclear complexes, the molecular structure confirms that the dithiocarbamato ligand is mainly acting as monodentate, with a second longer Au-S distance of 3.197 (PMe3), 2.944(4) (PPh3), and 2.968 A (CNR). Three phosphine complexes are emissive at 562 (PMe3), 528 (PPh3), and 605 nm (dppm), at 77 K. X-ray diffraction studies of the dppm derivative show gold-gold intramolecular contacts of 3.0972(9) A (3.2265(10) A for a second independent molecule) and basically monodentate coordination of the dithiocarbamato ligands. All the complexes extract sodium and potassium salts from aqueous solutions. The diphosphine derivatives are noticeably better extractors than the monophosphino derivatives, mainly for potassium salts.

Ruthenium hydride complexes with a heteroscorpionate ligand derived from methane: 2-phenoxy-bis(pyrazol-1-yl)methane. The hemilabile role of the ligand in substitution and proton transfer reactions

The complex [RuH(κ 3-bpzmPhO)(cod)] ( 1) was synthesized by the reaction of [RuH(cod)(NH 2NMe 2) 3][BPh 4] with the potassium salt of 2-phenoxy-bis(pyrazol-1-yl)methane (bpzmPhOK). This ligand adopts a κ 3- N, N, O coordination on the metal center that is reminiscent of the situation usually observed in trispyrazolylborate complexes. Complex 1 exists in solution as a mixture of two diastereoisomers that are in equilibrium. The reaction of 1 with different phosphines (PMe 3, PMe 2Ph, PMePh 2 and PPh 3) has been studied. The reaction product depends not only on the nature of the phosphine but also on the complex:L ratio and the temperature. Diphosphine derivatives of stoichiometries [RuH(κ 1- O-bpzmPhO)(cod)L 2] (L=PMe 3, PMe 2Ph) and [RuH(κ 3-bpzmPhO)L 2] (L=PMe 3, PMe 2Ph, PMePh 2, PPh 3) were prepared. Similarly, tetraphosphine derivatives of formula [ cis- O, H-RuH(κ 1- O-bpzmPhO)L 4] (L=PMe 3, PMe 2Ph) were obtained. The complex with PMe 2Ph can be transformed into the respective trans isomer by heating the solution. The reaction of 1 with five equivalents of PMe 3 gives rise to a pentaphosphine derivative with complete decoordination of the anionic bpzmPhO ligand. This ligand exhibits hemilabile behavior that involve a reversible coordination of the pyrazole fragments. Proton transfer reactions from HBF 4 to 1 have also been studied both in acetone-d 6 and in methanol-d 4. In all of these processes the proton is selectively transferred to the oxygen of the bpzmPhO ligand, which remains coordinated through at least the N-donor centers. Three hydride derivatives are formed in these reactions and they differ either in the relative orientation of the ligands or in the coordination of the OH group of the ligand.

Synthesis and characterisation of derivatives of [HIr 4(CO) 10(μ-PPh 2)] with mono and diphosphines; X-ray molecular structures of [HIr 4(CO) 8(PPh 3) 2(μ-PPh 2)] and [HIr 4(CO) 8{Ph 2P(CH 2) nPPh 2}(μ-PPh 2)] ( n=1 and 4)

The reactions of the cluster compound [HIr 4(CO) 10(μ-PPh 2)] ( 1) with a series of phosphines, PMe 3 and PPh 3, and diphosphines, Ph 2P(CH 2) nPPh 2 ( n=1, dppm, n=2, dppe and n=4, dppb) and cis-PPh 2CHCHPPh 2 (dppen), have been investigated. Reaction of 1 with PMe 3 yielded the mono and di-substituted derivatives [HIr 4(CO) 10− n (PMe 3) n (μ-PPh 2)] ( n=1, 2 and n=2, 3). 1H and 31P-NMR spectroscopy monitoring revealed that the two kinetic isomers 2b and 2c undergo conversion to the thermodynamic isomer 2a through a process, which apparently involves intra-molecular migration of the PMe 3 ligand. In contrast, analogous kinetic isomers were not detected during the synthesis of the PPh 3 derivative [HIr 4(CO) 9(PPh 3)(μ-PPh 2)] ( 4). According to 1H and 31P-NMR data, compounds [HIr 4(CO) 8(L) 2(μ-PPh 2)] (L=PMe 3 3 and PPh 3 5) exist in solution in three isomeric forms 3a– 3c and 5a– 5c, respectively, at −60 °C. Compound 1 also reacts with diphosphines to give CO substitution products, whose composition depends on the size of the methylene chain. Whilst reaction with dppm and dppen yields only the bi-substituted species [HIr 4(CO) 8(dppm)(μ-PPh 2)] ( 6) and [HIr 4(CO) 8(dppen)(μ-PPh 2)] ( 7), respectively, with dppb, both the dimeric compound [{HIr 4(CO) 9(μ-PPh 2)} 2(dppb)] ( 8a) and the monomeric species [HIr 4(CO) 8(dppb)(μ-PPh 2)] ( 8b) are formed, and with dppe, only the dimeric compound [{HIr 4(CO) 9(μ-PPh 2)} 2(dppe)] ( 9) is obtained. The dppm derivative exists in solution in the form of two inter-converting isomers 6a and 6b that differ with respect to the mode of coordination of the dppm and CO ligands. Isomerisation of 6a– 6b is proposed to involve intra-molecular migration of dppm and carbonyl ligands. Structures were proposed for all compounds, on the basis of 1H and 31P[ 1H]-NMR studies and of correlations previously established for the phosphine and diphosphine derivatives of [Ir 4(CO) 12]; the molecular structures of compounds 5c, 6a and 8b were established by X-ray diffraction studies which confirmed the structures proposed based on spectroscopic data.

Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex

The hydrogensulfido-bridged diiridium complex [ClCp*Ir(µ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(µ3-S)2 core [(Cp*Ir)2(µ3-S)2RuCl2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(µ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(µ3-S)2RuMe(dppe)][PF6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl2)Ir}(µ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(µ3-S)2(µ-H)2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(µ3-S)2RuCl(CO)(PPh3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(µ3-S)2RuCl(CNXy)(PPh3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(µ3-S)2Ru(CNXy)2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(µ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(µ3-S)2RuCl(depe)][BPh4] 4′, 5·CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.

Diphosphine derivatives of urea and thiourea

The reaction of (Me3Si)HNC(O)NH(SiMe3) or thiourea with PPh2Cl gave Ph2PHNC(E)NHPPh2(E = O I or S II) which may be oxidised at the phosphorus(III) centres to give Ph2P(E′)HNC(E)NHP(E′)Ph2(E = O, E′= O III, S IV or Se V; E = S, E′= S VI). Compound I forms simple chelate P,P′ complexes with platinum and palladium. The crystal structures of II·Me2SO IV and cis-[PdCl2{Ph2PNHCONHPPh2-P,P′}] have been determined.

Reactions of [Au(acac)PPh3] with diphosphine derivatives: different coordination modes of gold to the ligand systems. X-ray structure of [SPPh2C(AuPPh3)2PPh2CH(AuPPh3)COOMe]ClO4 and [Au5(C6F5)((SPPh2)2C)2(PPh3)]. [Erratum to document cited in CA119(19):203522v

ADVERTISEMENT RETURN TO ISSUEPREVArticleReactions of [Au(acac)PPh3] with diphosphine derivatives: different coordination modes of gold to the ligand systems. X-ray structure of [SPPh2C(AuPPh3)2PPh2CH(AuPPh3)COOMe]ClO4 and [Au5(C6F5)((SPPh2)2C)2(PPh3)]. [Erratum to document cited in CA119(19):203522v]M. Concepcion Gimeno, Antonio Laguna, Mariano Laguna, Federico Sanmartin, and Peter G. JonesCite this: Organometallics 1994, 13, 4, 1538Publication Date (Print):April 1, 1994Publication History Published online1 May 2002Published inissue 1 April 1994https://doi.org/10.1021/om00016a069RIGHTS & PERMISSIONSArticle Views85Altmetric-Citations6LEARN 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 (72 KB) Get e-Alerts Get e-Alerts

Reactions of [Au(acac)PPh3] with diphosphine derivatives: different coordination modes of gold to the ligand systems. X-ray structure of [SPPh2C(AuPPh3)2PPh2CH(AuPPh3)COOMe]ClO4 and [Au5(C6F5){(SPPh2)2C}2(PPh3)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of [Au(acac)PPh3] with diphosphine derivatives: different coordination modes of gold to the ligand systems. X-ray structure of [SPPh2C(AuPPh3)2PPh2CH(AuPPh3)COOMe]ClO4 and [Au5(C6F5){(SPPh2)2C}2(PPh3)]M. Concepcion Gimeno, Antonio Laguna, Mariano Laguna, Federico Sanmartin, and Peter G. JonesCite this: Organometallics 1993, 12, 10, 3984–3991Publication Date (Print):October 1, 1993Publication History Published online1 May 2002Published inissue 1 October 1993https://doi.org/10.1021/om00034a034RIGHTS & PERMISSIONSArticle Views283Altmetric-Citations40LEARN 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 (875 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

ChemInform Abstract: DIPHOSPHINE DERIVATIVES. PART VIII. TETRAPHENYLDIPHOSPHINE DIOXIDE AND TETRAPHENYLDIPHOSPHINE DISULPHIDE: STRUCTURE AND SKELETAL VIBRATIONS. PREPARATION OF DIPHENYLPHOSPHINODISELENOIC ANHYDROSELENIDE, PH2P(SE)SEP(SE)PH2

Chemischer InformationsdienstVolume 13, Issue 22 Physical Organic Chemistry ChemInform Abstract: DIPHOSPHINE DERIVATIVES. PART VIII. TETRAPHENYLDIPHOSPHINE DIOXIDE AND TETRAPHENYLDIPHOSPHINE DISULPHIDE: STRUCTURE AND SKELETAL VIBRATIONS. PREPARATION OF DIPHENYLPHOSPHINODISELENOIC ANHYDROSELENIDE, PH2P(SE)SEP(SE)PH2 A. J. BLAKE, A. J. BLAKESearch for more papers by this authorG. P. MCQUILLAN, G. P. MCQUILLANSearch for more papers by this authorI. A. OXTON, I. A. OXTONSearch for more papers by this authorD. TROY, D. TROYSearch for more papers by this author A. J. BLAKE, A. J. BLAKESearch for more papers by this authorG. P. MCQUILLAN, G. P. MCQUILLANSearch for more papers by this authorI. A. OXTON, I. A. OXTONSearch for more papers by this authorD. TROY, D. TROYSearch for more papers by this author First published: June 1, 1982 https://doi.org/10.1002/chin.198222053AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue22June 1, 1982 RelatedInformation

Diphosphine derivatives: Part VIII . Tetraphenyldiphosphine dioxide and tetraphenyldiphosphine disulphide: structure and skeletal vibrations. Preparation of diphenylphos-ph

The X-ray powder diffraction pattern for tetraphenyldiphosphine dioxide Ph 2P(O)P-(O)Ph 2 can be satisfactorily indexed on the assumption that the compound is isomorphous with tetraphenyldiphosphine disulphide. Calculated crystal data for the dioxide are: monoclinic, P2,/ c, a = 9.44(1), b = 15.62(3), c = 13 37(3) Å, β = 98.0(1)° Z = 4. The P—P stretch is assigned in the Raman spectrum of the disulphide at 536 cm −1 and in the dioxide at the unusually high frequency of 601 cm −21. The reaction of tetraphenyldiphosphine with KSeCN in acetonitrile leads to oxidation of the phosphorus and selenium insertion into the P—P bond, yielding Ph 2P(Se)SeP(Se)Ph 2, diphenylphosphinodiselenoic anhydroselenide, previously only identified in solution.

Diphosphine derivatives—I. The vibrational spectrum of tetramethyldiphosphine disulphide (tmps) and of tmps- d12 and tmps- 13C 4

The i.r. and Raman spectra of tetramethyldiphosphine disulphide (tmps) and of tmps-d 12 and tmps- 13C 4 are reported and the assignment of the skeletal modes is discussed. Raman polarization data confirm previous assignments for the PS and PP stretching modes and the symmetric PPS bend is assigned at Δν = 170 cm −1. There is no evidence of trans-gauche or trans-cis isomerism in solution: it is estimated that the molecule remains at least 99.5% in or very close to the trans form in chloroform or methylene chloride. The small dipole moment in benzene solution most probably arises from small distortions of the trans-structure, rather than trans-gauche isomerism. It has been suggested that the solid compound contains two significantly different types of tmps molecule but there is no evidence of this in the solid vibrational spectrum. Interactions between the skeletal and internal methyl vibrations are significant and are illustrated by the appreciable frequency shifts which occur in many of the skeletal modes in the deuterated compound.