Phosphorus-phosphorus Bond Research Articles

Reducing and Reversing the Diphosphene-Diphosphinylidene Energy Separation.

The dependence of the relative energies of 116 diphosphene and diphosphinylidene compounds on the modification of their structures is studied theoretically. Optimized geometries and relative energies are reported for all structures. With the purpose of investigating the effects of various substituents on the parent PPH2 and HPPH molecules, isodesmic reaction energies were obtained for single and double substitution. In the case of the substitution of both H atoms by lithoxy (OLi) or ONa groups is the diphosphinylidene type structure found to be lower in energy. For the lithoxy group, the energy difference amounts to 33 kcal/mol at CCSD(T) cc-pVTZ level of theory. This result is explained through the natural population analyses, where a very favorable Coulombic attraction is found in the OLi substituted diphosphinylidene structure. The order of the effectiveness of the substituents in lowering the relative energy of the diphosphinylidene structure is OLi > ONa > OH > OSiH3 > OCH3 > OPh > NH2 > N(CH3)2 > F > ONH2 > OBH2 > CH3 > OOH > Ph > BF2 > PH2 > SiH3 > SH > HC═O > Cl > CF3 > Br > SiF3 > NF2 > NO2 > C≡CH > OF > CN. Natural bond orbital (NBO) analysis explains other qualitative bonding features, for example, phosphorus-phosphorus bond orders as large as 2.5 for R2PP structures and as small as 1.6 for RPPR structures.

Organophosphorus Compounds; 124. Phosphorus-Phosphorus Bond Cleavage in Phosphorus-Carbon Cage Compounds Containing a Diphosphirane Moiety

The reactions of diphosphatricyclooctenes 9 with bromine (10 a) or iodine chloride (10 b) proceed by selective cleavage of the phosphorus-phosphorus bond of the diphosphirane unit with formation of the diphosphabicyclooctenes 11. On reaction of 11 a with one equivalent of nonacarbonyldiiron (12) metal complexation of one phosphorus center (→ 13 a) is achieved. The constitution of the η 1-complex 13 a was confirmed by X-ray crystallography.

Study on synthesis and herbicidal activity of heterocyclic compounds containing P-P bond

N,N′-diphenylurea reacted with phosphorus trichloride and phenyl dichlorophosphane giving the heterocyclic compounds 1 and 2 with a direct phosphorus-phosphorus bond (P-P bond), respectively. The new compounds were characterized by elementary analysis, NMR and IR spectra. The results of preliminary bioassay showed that these heterocycles possess selective herbicidal activity at 1.5 kg/hm2.

EXAFS and EELS evidence for the synthesis of a new amorphous nickel oxythiophosphate NiPS 2O

The room temperature synthesis of NiPS 3 by mixing a nickel salt and [Li 4 +(P 2S 6) 4−] in water from which oxygen has not been removed leads to an oxygenated phase. Nickel K edge X-ray absorption data and nickel L 2,3, phosphorus and sulfur K edges electron energy loss spectroscopy experiments show that a pure oxythiophosphate phase with a formulation close to NiPS 2O is obtained. This composition is explained by a partial oxidation of the pristine (P 2S 6) 4− anion, before reaction to form (P 2S 4O 2) 4−. The higher oxidized anions are destroyed by the breaking of the phosphorus-phosphorus bond.

Insertion of transition metals into the phosphorus-phosphorus bond of 1,2-dihydro-1,2-diphosphetes: toward the phosphorus analogs of metal dithiolene complexes

The insertion of NiL 2 (L=phosphine) into the P-P bond of 1,2,3,4-tetraphenyl-1,2-dihydro-1,2-diphosphete has been achieved via two methods. In the first, the P-P bond is initially cleaved with lithium and the derivatized dianion allowed to react with [NiCl 2 L 2 ]. The yields primarily a nickeladiphospholene with a distorted square-planar geometry.

Synthesis of Diphosphametallocene Derivatives of Divalent Lanthanides. Phosphorus-Phosphorus Bond Cleavage by Metallic Ytterbium and Samarium

Synthesis of Diphosphametallocene Derivatives of Divalent Lanthanides. Phosphorus-Phosphorus Bond Cleavage by Metallic Ytterbium and Samarium

Synthesis of Diphosphametallocene Derivatives of Divalent Lanthanides. Phosphorus-Phosphorus Bond Cleavage by Metallic Ytterbium and Samarium

Synthesis of Diphosphametallocene Derivatives of Divalent Lanthanides. Phosphorus-Phosphorus Bond Cleavage by Metallic Ytterbium and Samarium

ChemInform Abstract: Reaction of Dibenzylmercury with Secondary Phosphines: Phosphorus‐Phosphorus Bond Formation versus Benzyl Substitution.

ChemInformVolume 21, Issue 38 Organoelement Compounds ChemInform Abstract: Reaction of Dibenzylmercury with Secondary Phosphines: Phosphorus-Phosphorus Bond Formation versus Benzyl Substitution. J. T. YEH, J. T. YEH Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this authorL. R. AVENS, L. R. AVENS Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this authorJ. L. MILLS, J. L. MILLS Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this author J. T. YEH, J. T. YEH Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this authorL. R. AVENS, L. R. AVENS Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this authorJ. L. MILLS, J. L. MILLS Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this author First published: September 18, 1990 https://doi.org/10.1002/chin.199038263Read the full textAboutPDF 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. Volume21, Issue38September 18, 1990 RelatedInformation

THE REACTION OF DIBENZYLMERCURY WITH SECONDARY PHOSPHINES: FORMATION VERSUS BENZYL SUBSTITUTION

Abstract In an attempt to find a simple, high yield synthetic method to create a phosphorus-phosphorus bond from phosphorus-hydrogen bonds, we have investigated the reaction of dibenzylmercury DBM with secondary phosphines. The overall reaction is: DBM + R2PH→r toluene + Hg + R2P - PR2. Thus reaction of diphenylphosphine with DBM produces the desired coupled product tetraphenyldiphosphine in 85–90% yield. In contrast, the reaction of DBM with 1.3-bis(phenyIphosphino)propane Ph(H)P-(CH2)3-P(H)Ph produces the benzyl-substituted product Ph(Bz)P-(CH2)3-P(Bz)Ph rather than the expected cyclic compound 1,2-diphenyl-1,2-diphospholane PhP-(CH2)3-PPh. The dioxide or disulfide of Ph(H)P-(CH,),-P(H)Ph undergoes no reaction with DBM. The bulky 2.4,6-tris(tertbutyl) phenylphosphine ArPH, with DBM yields diastereomers of the coupled disecondary diphosphine Ar(H)P-P(H)Ar. The reaction of DBM with diphenylchlorophosphine results in a high yield of tetraphenyldiphosphine, but with phenyldichlorophosphine produces the benzyl-substituted product phenylbenzylchlorophosphine.

Reactions of secondary phosphines with a phosphorus-phosphorus bond and related reactions

Reactions of secondary phosphines with a phosphorus-phosphorus bond and related reactions

ChemInform Abstract: Multiple Bonding Involving Phosphorus. Some Recent Developments.

Abstract The first boraphosphene, (tmp)B=P(Ar) (tmp = 2,2,6,6-tetramethylpiperidino; Ar = 2,4,6-t-Bu3C6H2) has been prepared by thermolysis of the corresponding dimer, [(tmp)BP(Ar)]2 at 250°C. Mass spectral data are reported for (tmp)B=P(Ar) and ab initio MO calculations have been performed on the parent boraphosphene, HB=PH. The nature of the phosphorus-phosphorus bond in ArP=PAr has been investigated by solid state 31P NMR. The reactivity of the phosphavinylidene, [Mo(CO)2(n1−P=C(SiMe3)2(n-C5H5)] has been explored. The reaction of ArPCl2 with Na2[(n-C5H5)-V(CO)3] affords [V2(CO)4(n-C5H5)2{μ-PAr}], the first example of a group 5 phosphinidene complex.

Multiple Bonding Involving Phosphorus; Some Recent Developments

Abstract The first boraphosphene, (tmp)B=P(Ar) (tmp = 2,2,6,6-tetramethylpiperidino; Ar = 2,4,6-t-Bu3C6H2) has been prepared by thermolysis of the corresponding dimer, [(tmp)BP(Ar)]2 at 250°C. Mass spectral data are reported for (tmp)B=P(Ar) and ab initio MO calculations have been performed on the parent boraphosphene, HB=PH. The nature of the phosphorus-phosphorus bond in ArP=PAr has been investigated by solid state 31P NMR. The reactivity of the phosphavinylidene, [Mo(CO)2(n1−P=C(SiMe3)2(n-C5H5)] has been explored. The reaction of ArPCl2 with Na2[(n-C5H5)-V(CO)3] affords [V2(CO)4(n-C5H5)2{μ-PAr}], the first example of a group 5 phosphinidene complex.

ChemInform Abstract: PHOSPHORUS‐PHOSPHORUS BOND CLEAVAGE IN THE CAGE MOLECULE P4S3: SYNTHESIS AND CRYSTAL STRUCTURE OF THE TRINUCLEAR PLATINUM COMPLEX TRIS(2,6,7‐TRITHIA‐1,3,4,5‐TETRAPHOSPHABICYCLO(2.2.1)HEPTANE‐3,5‐DIYL‐P5,μ‐P# 3)TRIS(TRIPHENYLPHOSPHINEPLATINUM)‐BENZENE(1/1)

Chemischer InformationsdienstVolume 16, Issue 23 Organoelement Compounds ChemInform Abstract: PHOSPHORUS-PHOSPHORUS BOND CLEAVAGE IN THE CAGE MOLECULE P4S3: SYNTHESIS AND CRYSTAL STRUCTURE OF THE TRINUCLEAR PLATINUM COMPLEX TRIS(2,6,7-TRITHIA-1,3,4,5-TETRAPHOSPHABICYCLO(2.2.1)HEPTANE-3,5-DIYL-P5,μ-P# 3)TRIS(TRIPHENYLPHOSPHINEPLATINUM)-BENZENE(1/1) M. DI VAIRA, M. DI VAIRASearch for more papers by this authorM. PERUZZINI, M. PERUZZINISearch for more papers by this authorP. STOPPIONI, P. STOPPIONISearch for more papers by this author M. DI VAIRA, M. DI VAIRASearch for more papers by this authorM. PERUZZINI, M. PERUZZINISearch for more papers by this authorP. STOPPIONI, P. STOPPIONISearch for more papers by this author First published: June 11, 1985 https://doi.org/10.1002/chin.198523305Read the full textAboutPDF 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 onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume16, Issue23June 11, 1985 RelatedInformation

Oxidative Knüpfung einer Phosphor-Phosphor-Bindung unter Einwirkung von Ag(I)- bzw. Cu(II)-Ionen: Synthese und Struktur von [(C6H5)PH2Ag{μ-(C6H5PH)2}]2 (AsF6)2, einem sechsgliedrigen Silber-Phosphor-Ring / The Oxidative Formation of a Phosphorus-Phosphorus Bond in the Presence of Ag(I) and Cu(II) Ions: Synthesis and Structure of [(C6H5)PH2Ag{μ-(C6H5PH)2}]2 (AsF6)2, Containing a Six-Membered Silver-Phosphorus Ring

Abstract The reaction between AgAsF6 and phenylphosphine proceeds with formation of a phosphorus-phosphorus bond. The main product 1, [(C6H5)PH2Ag{μ-(C6H5PH)2}]2 (AsF6)2, was characterized by an X-ray structure determination [P1̄, a = 919.0(4), b = 1109.8(4), c = 1316.4(5) pm, α = 97.48(3), β = 107.25(3), γ = 102.71(3)°, Z = 1, R = 0.057 for 2806 observed reflections], 1 contains Ag2P4 rings; the silver atoms are further coordinated by phenylphosphine ligands, thus acquiring trigonal coordination geometry. A similar reaction is observed with Cu(AsF6)2, forming the analogous Cu(I) complex 2.

ChemInform Abstract: UNPRECEDENTED OXIDATIVE ADDITION OF THE P4S3 CAGE MOLECULE WITH PHOSPHORUS‐PHOSPHORUS BOND CLEAVAGE: SYNTHESIS AND STRUCTURE OF (IR(μ‐P4S3)(PPH3)CL(CO))2

Chemischer InformationsdienstVolume 15, Issue 6 Organoelement Compounds ChemInform Abstract: UNPRECEDENTED OXIDATIVE ADDITION OF THE P4S3 CAGE MOLECULE WITH PHOSPHORUS-PHOSPHORUS BOND CLEAVAGE: SYNTHESIS AND STRUCTURE OF (IR(μ-P4S3)(PPH3)CL(CO))2 C. A. GHILARDI, C. A. GHILARDISearch for more papers by this authorS. MIDOLLINI, S. MIDOLLINISearch for more papers by this authorA. ORLANDINI, A. ORLANDINISearch for more papers by this author C. A. GHILARDI, C. A. GHILARDISearch for more papers by this authorS. MIDOLLINI, S. MIDOLLINISearch for more papers by this authorA. ORLANDINI, A. ORLANDINISearch for more papers by this author First published: February 7, 1984 https://doi.org/10.1002/chin.198406300Read the full textAboutPDF 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 onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume15, Issue6February 7, 1984 RelatedInformation

Unprecedented Oxidative Addition of the P4S3 Cage Molecule with Phosphorus-Phosphorus Bond Cleavage. Synthesis and Molecular Structure of [Ir(?-P4S3) (PPh3) Cl(CO)

Angewandte Chemie International Edition in EnglishVolume 22, Issue S10 p. 1066-1074 Communication Unprecedented Oxidative Addition of the P4S3 Cage Molecule with Phosphorus-Phosphorus Bond Cleavage. Synthesis and Molecular Structure of [Ir(μ-P4S3) (PPh3) Cl(CO)]2 Dr. Carlo A. Ghilardi, Dr. Carlo A. Ghilardi Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Search for more papers by this authorDr. Stefano Midollini, Dr. Stefano Midollini Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Search for more papers by this authorDr. Annabella Orlandini, Corresponding Author Dr. Annabella Orlandini Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Search for more papers by this author Dr. Carlo A. Ghilardi, Dr. Carlo A. Ghilardi Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Search for more papers by this authorDr. Stefano Midollini, Dr. Stefano Midollini Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Search for more papers by this authorDr. Annabella Orlandini, Corresponding Author Dr. Annabella Orlandini Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, 27 Via F. D. Guerrazzi, I-50132 Firenze (Italy)Search for more papers by this author First published: October 1983 https://doi.org/10.1002/anie.198310660Citations: 3AboutPDF 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.Citing Literature Volume22, IssueS10Supplement: Complete manuscripts of selected Communications in issue 10/1983October 1983Pages 1066-1074 RelatedInformation

Darstellung und Reaktionen von bicyclischen Verbindungen mit einer Phosphor-Phosphor-Bindung/Preparation and Reactions of Bicyclic Compounds with a Phosphorus-Phosphorus-Bond

Abstract The reaction of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea with PCl3 leads to the bicyclic compound OP2[MeNCONMe]2 (3) with a direct phosphorus-phosphorus bond and to the bicycle MeNP2[MeNCONMe]2 (4). 3 reacts with tetrachloro-o-benzoquinone (TOB) to yield the spirocycle Ce6Cl4tMeNCONMe]2P2O (5) with a λ4P-λ5P-bond. The Lewis acids SbCl5 and SnCL4 react with 3 to give the adducts 6 and 7. The reactions of 3 with the metal carbonyls Fe2(CO)9, Cr(CO)5THF and Cr(CO)4C7H8 lead to the metal complexes 8-10. The compounds were characterized on the basis of 31P NMR and mass spectra.

Reactions of phosphorus fluorides and ortho-carborane ditertiary aminophosphines

Fluorophosphine bidentate ligands containing o-carborane as backbone can be prepared by the reaction of the lithium- o-carboranes and PF 2X derivatives to give only two species: the unsymmetrical (C 6H 5) 2P[B 10H 10C 2]PF 2 and the cyclic FP[B 10H 10C 2] 2PF, both in low yield. However, exchange of F and NMe 2 groups by use of PF 5 or PF 3 provides a facile way to produce several new fluorophosphines. Phosphorus pentafluoride forms solid adducts with the o-phosphino derivatives (C 6H 5) 2P[B 10H 10C 2]P(NMe 2) 2, (Me 2N) 2P[B 10H 10C 2]P(NMe 2) 2 and (C 6H 5) 2P[B 10H 10C 2]H. All the adducts contain a phosphorus-phosphorus bond as evidenced from i.r., NMR and stoichiometry. The stability of the adducts reflects the strength of the PP bond formed upon complexation. When suspensions or solutions of the adducts are heated they exchange F and NMe 2 groups and no redox occurs. The products (C 6H 5) 2P[B 10H 10C 2]P(F)NMe 2(I) and Me 2N(F)P[B 10H 10C 2]P(F)NMe 2(II) react further with PF 5 giving (C 6H 5) 2P[B 10H 10C 2]PF 2(III) and F 2P[B 10H 10C 2]PF 2(IV). The precursors also react with phosphorus trifluoride to produce only (I) and (Me 2N) 2P[B 10H 10C 2]P(F)NMe 2(V) regardless of the reaction conditions. All the products I–V have been identified by 1H, 19F, and 31P NMR and i.r. spectroscopy, mass spectrometry, and elemental analysis. The NMR spectra of the novel (IV) have been analysed as X 2AA 1X 1 2 spin system.

Synthesis and dynamic nuclear magnetic resonance studies of the heterocyclic diphosphacyclopolysilanes, (PhP)2(SiMe2)n. Crystal and molecular structure of (PhP)2(SiMe2)3

Abstract The heterocyclic diphosphasilanes (PhP)2(SiMe2)n(n - 2, 3, 4) were synthesized by the reactions of 1, 2-dilithium-1, 2-diphenyldiphosphide with α, ω-dichloropermethylpolysilanes Cl(SiMe2)nCl (n - 2, 3, 4). Stereochemical fluxionality in these compounds was examined by dynamic nuclear magnetic resonance. The1H, 13C, 31P and29Si NMR spectra are reported and discussed in terms of a phosphorus inversion mechanism. Values of the free energy of activation for phosphorous inversion are reported for (PhP)2(SiMe2)n (n - 3, 4) and compared with related compounds. A single-crystal X-ray structure analysis has been carried out on (PhP)2-(SiMe2)3. The material crystallizes in the monoclinic space groupP21/c with four molecules per unit cell. The cell dimensions area - 12.526(11)A˚, b - 11.828(10)A˚, c - 15.412(7)A˚and β - 103.56(6)°. The molecule exists in thedl (trans) form with the five-membered ring significantly twisted. The angle between the phosphorus-phosphorus bond and the plane of the three silicon atoms is 42.9°.

Appearance and ionization potentials of ions produced by electron-impact on some phosphorus-fluorine compounds: the phosphorus-phosphorus bond dissociation energy in diphosphorus tetrafluoride

The ionization potentials of P2F4, PF3 PF2H and PF2I and the appearance potentials of the PF+2 ion from these species are reported. The ionization potential of the PF2˙ radical is estimated using approximations for the PF2—X (X = F, I and H) bond dissociation energies. The P—P bond dissociation energy in diphosphorus tetrafluoride is estimated as 57 ± 10 kcal mol–1.