- Platinum(II) complexes of some unsymmetrical diphosphenes
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Reaction of the unsymmetrical diphosphene Ar*P=PArF1 (Ar*?=?2,4,6-tBu3C6H2, ArF?=?2,4,6-(CF3)3C6H2) with the dimeric platinum(II) species trans-[Pt(PEt3)Cl(μ-Cl]2led initially to the formation of two different monomeric Pt(II) complexes trans-[Pt(PEt3)Cl2(Ar*P=PArF)] 2 and trans-[Pt(PEt3)Cl2(ArFP=PAr*)] 3, where the underlined phosphorus atom coordinates to Pt. These were readily identifiable by31P NMR solution-state spectroscopy, but attempts to separate them by column chromatography were unsuccessful. When the reaction was repeated on a larger scale, a third complex cis-[Pt(PEt3)Cl2(ArFP=PAr*)] 4 was detected in solution, with P-ArFbound to Pt. Calculations of energies and31P NMR chemical shifts confirm that this species is expected to be the thermodynamically most stable monomeric reaction product. For comparison, we have also prepared the analogous Pt(II) complex trans-[Pt(PEt3)Cl2(Ar*P=PAr*)] 6 of the symmetrical diphosphene Ar*P=PAr* 5, and obtained its31P NMR parameters in solution. The mixed diphosphene Ar′P=PArF7 (Ar′?=?2,6-(CF3)2C6H3) reacts with the same platinum(II) dimer to yield a single cis-complex 8. Calculations have enabled us to assign the31P chemical shifts of this unsymmetrical diphosphene 7, and to show that the Ar′ group is coordinated to Pt in the unique product cis-[Pt(PEt3)Cl2(Ar′P=PArF)] 8.
- Dillon, Keith B.,Fox, Mark A.,Gibson, Vernon C.,Goodwin, Helen P.,Sequeira, Leila J.
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p. 113 - 119
(2017/02/05)
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- Isolation of a Highly Persistent Diphosphanyl Radical: The Phosphorus Analogue of a Hydrazyl
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Stable for at least one week below -30°C: crystals of 1, the first highly persistent diphosphanyl radical, have been isolated and characterized. This phosphorus-centered radical exhibits hyperfine coupling whose anisotropy is considerably larger than that for well-established nitrogen radicals (hydrazyls nitroxides). This feature is of potential interest for studies of fast molecular movements. Mes =2,4,6-tBu3C6H2.
- Loss, Sandra,Magistrato, Alessandra,Cataldo, Laurent,Hoffmann, Stefan,Geoffroy, Michel,Roethlisberger, Ursula,Gruetzmacher, Hansjoerg
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p. 723 - 726
(2007/10/03)
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- Synthesis and redox properties of a diphosphene carrying a redox-active sterically protecting group
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The 2,6-dimesityl-4-[bis(4-methoxyphenyl)amino]phenyl group was developed as a sterically protecting group carrying a reversible redox site at the 4-position and was applied to the construction of a novel redox system composed of the diphosphene and triarylamine units.
- Tsuji, Kyoko,Sasaki, Shigeru,Yoshifuji, Masaaki
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p. 3203 - 3206
(2007/10/03)
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- Application of 1,2-bis(2-bromo-3,5-di-t-butylphenyl)ethane to preparation of compounds having two diphosphene units
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A sterically crowded bromobenzene, 1,2-bis(2-bromo-3,5-di-t-butylphenyl)ethane, was prepared and converted to the corresponding phosphonous dichloride, which reacted with lithium (2,4,6-tri-t-butylphenyl)phosphide to give 1,2-bis[3,5-di-t-butyl-2-{(2,4,6-
- Yoshifuji, Masaaki,Shinohara, Naoyuki,Toyota, Kozo
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p. 7815 - 7818
(2007/10/03)
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- Transition-metal Catalysed Metathesis of Phosphorus-Phosphorus Double Bonds
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W(PMe3)6 is an efficient chloride ion abstracting reagent for the synthesis of RP=PR species from RPCl2 precursors; moreover, the W(PMe3)6-RPCl2 solutions catalyse the exchange of the diphosphene PR end-groups via a mechanism closely related to the olefin metathesis process.
- Dillon, Keith B.,Gibson, Vernon C.,Sequeira, Leela J.
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p. 2429 - 2430
(2007/10/03)
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- GENERAL APPROACHES TO PHOSPHINIDENES VIA RETROADDITIONS
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Retroadditions - thermal and photochemical decomposition of phosphiranes and 3-phospholenes - offer general routes to free phosphinidenes.
- Li, Xinhua,Lei, Deqing,Chiang, Michael Y.,Gaspar, Peter P.
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- Sonochemistry in the diphosphirane series
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Sonication improves substantially the rate of formation of diphosphene 1 with respect to standard procedures. The cyclopropanation of 1 using sonochemical generation of methylene or halogeno-carbenes constitutes an interesting alternative in the diphosphi
- Etemad-Moghadam,Rifqui,Layrolle,Berlan,Koenig
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p. 5965 - 5968
(2007/10/02)
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- SOME NEW PROTECTIVE GROUPS FOR STABILIZING LOW COORDINATED PHOSPHORUS COMPOUNDS
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Sterically stabilized diphosphenes and 1,3-diphosphaallenes by 2,4-di-t-butylphenyl or 2,4,6-tri-t-pentylphenyl groups were prepared.
- Yoshifuji, Masaaki,Sasaki, Shigeru,Shiomi, Daisuke,Niitsu, Takashi,Inamoto, Naoki
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p. 325 - 328
(2007/10/02)
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- Synthesis and Structures of Phosphinidene and Phosphido Complexes of Iron and Cobalt
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Treatment of Na with R1PCl2 (R1=2,4,6-But3C6H2) result in a dicobalt phosphinidene complex, 1)>, of the 'open' type containing a trigonal-planar phosphorus, no metal-metal bond, and some degree of Co-P multiple bonding as established by an X-ray diffraction study.The attempted synthesis of di-iron phosphinidene complexes via the reaction of 2 with dichlorophosphines RPCl2 failed to produce an isolable species containing the desired phosphinidene fragment.For R=(Me3Si)2CH a large number of products were formed, two of which were isolated and identified within the same crystal structure by X-ray crystallography.Both complexes were found to contain a di-iron centre bridged by a phosphido ligand: > and di-nuclear iron species were observed by (31)P n.m.r. spectroscopy, these being 1)2>, t2>>>, 1)>, and also the diphosphine R1PHPHR1.In addition to the synthetic and structural studies, extended Hueckel molecular orbital calculations have been carried out on model phosphidine complexes in a attempt to understand their electronic and structural features.
- Arif, Atta M.,Cowley, Alan H.,Pakulski, Marek,Pearsall, Mary-Ann,Clegg, William,et al.
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p. 2713 - 2722
(2007/10/02)
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- Wavelength- and Temperature-dependent Photolysis of a Diphosphene. Generation of 2,4,6-Tri-t-butylphenylphosphinidene and E/Z Isomerization
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A phospha-indane derivative was obtained via intramolecular C-H insertion of the phosphinidene generated as an intermediate by the photolysis of E-1,2-bis(2,4,6-tri-t-butylphenyl)diphosphene whereas the photolysis through a Pyrex filter at -40 o/sup
- Yoshifuji, Masaaki,Sato, Takahiro,Inamoto, Naoki
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p. 1735 - 1738
(2007/10/02)
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- Photochemie von pentamethylcyclopentadienyl-substituierten Diphosphenen und Phosphaarsenen
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Under irradiation dimerization of the diphosphenes Cp*P=PCp* and Cp*P=PR (Cp* = Pentamethylcyclopentadienyl, R = 2,4,6-Tri-t-butylphenyl) and the phosphaarsene Cp*As=PR takes place.Further irradiation leads to homolytic cleavage of Cp*-element bonds.Intramolecular recombination leads to the bicyclic butterfly-compounds P4R2 and P2As2R2.
- Jutzi, P.,Meyer, U.
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p. C18 - C20
(2007/10/02)
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- SYNTHESIS OF TWO STABLE DIPHOSPHENES WITH A NEW STABILIZING SUBSTITUENTS
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Two new diphosphenes 7 and 10 have been synthesized by action of DBU on trichlorogermylphosphines 4 and 8; this route involves the intermediate formation of chlorophosphines 5 and 9.Diphoshenes 7 and 10 are stabilized by the 2,6-bis(trifluoromethyl)phenyl
- Escudie, Jean,Couret, Claude,Ranaivonjatovo, Henri,Lazraq, Mohamed,Satge, Jaques
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- PHOSPHORUS-PHOSPHORUS SINGLE OR DOUBLE BOND FORMATION FROM PCl(3-n)Rn (n=1 or 2) AND A BIS-IMIDAZOLIDINE REDUCING AGENT
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1,3,1'.3'-Tetraethyl-bis(2,2'-imidazolidene), L2Et (I), is a mild homogeneous reducing agent which reduces P-Cl bonds phosphonous or phosphinous chlorides to give compounds with phosphorus-phosphorus bonds.High yields of diphosphines P2R4 are produced from the corresponding phosphinous chlorides (PClR2).Phenyl- and t-butyl-phosphonous dichlorides are reduced to cyclopolyphosphines (PR)n, which appear to be the kinetically controlled products. 2,4,6-Tri(t-butyl)phenylphosphonous dichloride (PArCl2) is reduced to either 1,2-dichloro-1,2,bis(2,4,6-tri-t-butylphenyl)diphosphine (PArCl)2 or trans-bisdiphosphene (P2Ar2) depending on the initial stoichiometry.
- Goldwhite, Harold,Kaminski, John,Millhauser, Glenn,Ortiz, Jesus,Vargas, Maurice,et al.
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-
- QUELQUES PROPRIETES CHIMIQUES DU TRIS(TERTIOBUTYL)-2,4,6 PHENYLDITHIOPHOSPHORANE
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The chemical properties of the dithiometaphosphonate analogue, tris(2,4,6-t-butyl)phenyldithiophosphorane (1), are reported in detail.
- Navech, J.,Revel, M.,Kraemer, R.,Mathieu,S.
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- SILICIUMVERBINDUNGEN MIT STARKEN INTRAMOLEKULAREN STERISCHEN WECHSELWIRKUNGEN XII. SYNTHESE UND MOLEKUELSTRUKTUR DES 1,2-BIS(2,4,6-TRI-t-BUTLYPHENYL)-3,3-DI-t-BUTYL-1,2,3-DIPHOSPHASILIRANS
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The reaction of di-t-butyldiiodosilane with excess lithium naphthalenide followed by treatment with dichloro(2,4,6-tri-t-butylphenyl)phosphane (ArPCl2) leads to the diphosphene ArP=Ar, the air-stable compound 1,2-bis(2,4,6-tri-t-butylphenyl)-3,3-di-t-butyl-1,2,3-diphosphasilirane (3), and other products.The X-ray structure analysis reveals slightly elongated Si-P and P-P bond lengths of about 224.3 and 223.4 pm, respectively.The steric crowding of the three-membered heterocycle causes a puckering of the phenyl rings and a bending of the ortho-t-butyl groups out of the ring planes.
- Weidenbruch, Manfred,Herrndorf, Marlies,Schaefer, Annemarie,Peters, Karl,Schnering, Hans Georg von
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- ETUDE DE LA REACTIVITE DU TRIS(TERTIOBUTYL)PHENYLDITHIOPHOSPHORANE
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Heating of tris(tertiobutyl)phenyldithiophosphorane gives rise to an isomer with a tetracoordinated phosphorus atom.The action of triphenylphosphine loads to a tricyclophosphathiane which can be transformed in diphosphene by an excess of triphenylphosphine.Reactions with various nucleophilic derivatives (pyridine, triethylamine, diethylamine, butylamine, water, tetraphenylarsonium chloride) are described.
- Navech, J.,Revel, M.,Kraemer, R.
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p. 207 - 210
(2007/10/02)
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- ATTEMPTED ISOLATION OF MONOMERIC IMINOPHOSPHINES. FORMATION OF A STERICALLY PROTECTED IMINOPHOSPHINE P-SULFIDE AND DETECTION OF IMINOPHOSPHINES
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A monomeric iminophosphine was observed by the desulfurization of the corresponding P-sulfide; the structure of the sulfide was discussed in terms of ab initio calculation; several attempts to isolate sterically protected iminophosphines were described.
- Yoshifuji, Masaaki,Shibayama, Katsuhiro,Toyota, Kozo,Inamoto, Naoki,Nagase, Shigeru
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p. 237 - 240
(2007/10/02)
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- REACTION OF DIPHOSPHENES WITH ELEMENTAL SELENIUM. ISOLATION AND CHARACTERIZATION OF SELENADIPHOSPHIRANES AND DESELENOXOPHOSPHORANE
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Sterically protected thermally stable 1,2,3-selenadiphosphirane and diselenoxophosphorane were isolated from the reaction of E-bis(2,4,6-tri-t-butylphenyl)diphosphene with elemental selenium.
- Yoshifuji, Masaaki,Shibayama, Katsuhiro,Inamoto, Naoki
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p. 603 - 606
(2007/10/02)
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- The P=P Stretching Frequency Observed in the Resonance Raman Spectrum of Bis(2,4,6-tri-tert-butylphenyl)diphosphene
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The frequency of the P=P double bond stretching has been obtained for the first time from a resonance Raman study of bis(2,4,6-tri-tert-butylphenyl)diphosphene.
- Hamaguchi, Hiro-o,Tasumi, Mitsuo,Yoshifuji, Masaaki,Inamoto, Naoki
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p. 508 - 509
(2007/10/02)
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- ISOLATION AND CHARACTERIZATION OF A STABLE DITHIOXOPHOSPHORANE
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A sterically protected dithioxophosphorane, 2,4,6-tri-t-butylphenyldithioxophosphorane, has been isolated and characterized for the first time as a stable compound.
- Yoshifuji, Masaaki,Toyota, Kozo,Ando, Kaori,Inamoto, Naoki
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p. 317 - 318
(2007/10/02)
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- STABLE UNSYMMETRICAL DIPHOSPHENES
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Variation of the ortho-alkyl substituents in diaryldiphosphenes revealed that their stability is determined by steric hindrance.By suitable combinations of ortho-substituents, it was therefore possible to prepare the first relatively stable unsymmetrical
- Smit, C.N.,van der Knaap, Th.A.,Bickelhaupt, F.
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p. 2031 - 2034
(2007/10/02)
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- Reaction of the Diphosphene ArP=PAr (Ar = 2,4,6-But3C6H2) with Sulphur: Isolation and X-Ray Structure of the Diphosphene Monosulphide
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The diphosphene ArP=PAr (Ar = 2,4,6-But3C6H2) reacts with elemental sulphur to give the stable monosulphide ArP(S)=PAr (2) whose structure was confirmed by an X-ray analysis; when treated with hexamethylphosphorous triamide, (2) reverts to the starting diphosphene but thermal and photochemical isomerisation of (2) gives the thiadiphosphirane Ar-cyclo-Ar.
- Yoshifuji, Masaaki,Shibayama, Katsuhiro,Inamoto, Naoki,Hirotsu, Ken,Higuchi, Taiichi
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p. 862 - 863
(2007/10/02)
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- STANNYLENE AND GERMYLENE AS POWERFUL DECHLORINATED REAGENTS. NEW ROUTE TO DIPHOSPHENE.
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Dichlorophosphines RPCl2 are reduced to the corresponding phosphorus-I compounds by the stannylene Me2Si(NtBu)2Sn: (1) or by the germylene GeI2 (2); in the case of the reaction of (5) with (1), bis(2,4,6-tri-tert-
- Veith, Michael,Huch, Volker,Majoral, Jean-Pierre,Bertrand, Guy,Manuel, Georges
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p. 4219 - 4222
(2007/10/02)
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- Generation and E.S.R. Spectra of Some New Phosphorus-centred Radicals P.2Ar2X, P.(Ar)X, P.(OAr)2, P.Ar2(:O), P.Ar(:NSiMe3), and .- derived from the Bulky Group C6H2Bu
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The photochemical reaction of X2 and the diphosphene trans-ArP=PAr (Ar = C6H2But3), (1), leads successively to P.2Ar2X, (2), P.(Ar)X, (3), and upon cooling 2 t, ΔHdiss = 107 +/- 7
- Cetinkaya, Bekir,Hudson, Andrew,Lappert, Michael F.,Goldwhite, Harold
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p. 609 - 610
(2007/10/02)
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- Synthesis and Characterisation of 2,4,6-Tri-t-Butylphenylphosphines; X-Ray Structure of t3-2,4,6)S>3
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Whereas treatment of phosphorus(III) chloride with an equimolar portion of LiAr (Ar = C6H2But3-2,4,6) affords PArCl2, with 2LiAr there is obtained ArP=PAr, which has low-lying MO's (photoelectron spectroscopy) and a LUMO (reversible electrochem
- Cetinkaya, Bekir,Hitchcock, Peter B.,Lappert, Michael F.,Thorne, Andrew J.,Goldwhite, Harold
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p. 691 - 693
(2007/10/02)
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- A NEW ROUTE TO BIS(2,4,6-TRI-TERT-BUTYLPHENYL)DIPHOSPHENE VIA SILYLATED COMPOUND
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A new synthesis of stable diphosphene is reported. δ31P value is reinvestigated.
- Bertrand, Guy,Couret, Claude,Escudie, Jean,Majid, Samia,Majoral, Jean-Pierre
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p. 3567 - 3570
(2007/10/02)
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