- New Adamantane-like Silicophosphate Cage and Its Reactivity toward Tris(pentafluorophenyl)borane
-
The condensation reaction between Ph2Si(OC(O)CH3)2 and OP(OSiMe3)3 leads to elimination of CH3C(O)OSiMe3 and the formation of the new silicophosphate cage molecule Ph12Si6P4O16 (1) with an adamantane-like core possessing four terminal P=O moieties and six O-SiPh2-O bridging groups. Compound 1 was further reacted with the Lewis acid B(C6F5)3. We observed adduct formation by coordination through the P=O→B bonds and isolated and structurally characterized two new molecules. In the first of them, the adamantane-like cage is preserved and three phosphoryl oxygen atoms coordinate to boranes, forming Ph12Si6O16P4·3B(C6F5)3 (2); the remaining P=O group is inverted toward the cage center pointing along a C3 molecular axis. The molecule is chiral, and the compound 2 crystallizes as a conglomerate of homochiral crystals. Enantiomers 2M and 2P were both structurally characterized. The second adduct resulted from an unexpected reorganization of the Si-O-P linkages in the adamantane cage during the reaction of 1 with 4 equiv of B(C6F5)3. The bis-adduct Ph6Si3O8P2·2B(C6F5)3 (3) was formed with an inorganic core representing half of the parent molecule 1.
- Styskalik, Ales,Babiak, Michal,Machac, Petr,Relichova, Bohuslava,Pinkas, Jiri
-
-
Read Online
- Synthesis and Characterization of Silylated Phosphonium [P(OSiMe3)4]+ and Phosphate [O2P(OSiMe3)2]- Salts
-
Starting from an optimized synthesis of silylated phosphoric acid, OP(OSiMe3)3, a borate salt bearing the [P(OSiMe3)4]+ cation was generated in the reaction of OP(OSiMe3)3 with [Me3Si-H-SiMe3][B(C6F5)4], isolated, and fully characterized. Analogously to the protonated species, phosphoric acid (H3PO4) reaction of OP(OSiMe3)3 with a base led to the formation of the unknown [O2P(OSiMe3)2]- anion, which could be crystallized as potassium salt and structurally characterized, too. Both [P(OSiMe3)4]+ and [O2P(OSiMe3)2]- can be regarded as the formal autoprotolysis products of OP(OSiMe3)3.
- Felgenhauer, Paul,Labbow, René,Schulz, Axel,Villinger, Alexander
-
-
Read Online
- Nonaqueous synthesis of molecular zinc amide phosphate
-
Three new molecular zinc compounds were prepared by nonaqueous reactions of Zn[N(SiMe3)2]2 and ZnEt2 with trimethylsilylesters of phosphoric acid, OP(OSiMe3)3 and OP(OSiMe3)2(OH). Single-crystal X-ray diffraction analyses of crystalline products revealed molecular structures of two mononuclear complexes [ZnX2OP(OSiMe3)3] (X = N(SiMe 3)2 (1), hfacac = hexafluoroacetylacetonate, (2)) and one dinuclear zinc phosphate [(Zn{(py)N(SiMe3)2} {μ2-O2P(OSiMe3)2})2] (3). Compound 1 is only the second structurally characterized adduct of zinc bisamide with an oxygen donor and a three-coordinate Zn atom. The cyclic inorganic core {Zn(μ2-O2PO2)}2 in 3 is a model for the most common single four-ring (S4R) building unit of open-framework zinc phosphates. The molecule of 3 possesses reactive amide and trimethylsiloxy groups that can be employed in further studies on the formation of extended structures by condensation reactions. Spectroscopic properties and thermal behavior of the molecular products were examined. Compounds 1 and 3 were converted to α-Zn2P2O7 by calcination.
- Chyba, Jan,Moravec, Zdenek,Necas, Marek,Mathur, Sanjay,Pinkas, Jiri
-
-
Read Online
- High throughput screening under zinc-database and synthesis a dialkylphosphinic acid as a potential Kari inhibitor
-
A novel phosphorus derivative was synthesized through HTVS. The title compounds were confirmed by MS, 1H NMR, 31P NMR. The DOCK was also studied. Copyright Taylor & Francis Group, LLC.
- Liu, Xing-Hai,Chen, Pei-Quan,Guo, Wan-Cheng,Wang, Su-Hua,Li, Zheng-Ming
-
-
Read Online
- Preparation method of phosphate or phosphite and secondary battery. (by machine translation)
-
The preparation method of the phosphate or phosphite ester disclosed by the invention comprises, the following steps: of: reacting inorganic phosphate or inorganic phosphite 3) with a phosphoric acid ester as shown in a formula (shown in the 1) formula); and preparing 2) the phosphate ester or the. phosphite. ester according to the invention as shown in the invention . (by machine translation)
- -
-
Paragraph 0075; 0077
(2019/12/25)
-
- Method for synthesizing tri(trihydrocarbyl silicon) phosphate
-
The invention discloses a method for synthesizing tri(trihydrocarbyl silicon) phosphate. The method comprises the following steps: putting hexahydrocarbyl disiloxane and phosphoric acid into a reaction kettle, and carrying out a dehydration reaction under conditions of heating, stirring and backflow condensation; further carrying out a distillation reaction on trihydrocarbyl silicon amino, and carrying out vacuum distillation on a reaction liquid after amino is completely evaporated off, thereby obtaining the tri(trihydrocarbyl silicon) phosphate. The method for synthesizing the tri(trihydrocarbyl silicon) phosphate is easy in raw material obtaining and in addition has the characteristics of being high in conversion rate and yield; the method disclosed by the invention is simple in processroute, safe and environemtally friendly, low in consumption and small in waste emission, a tri(trihydrocarbyl silicon) phosphate product obtained from reactions is high in purity, and requirements ofa lithium ion electrolyate additive can be met.
- -
-
Paragraph 0043; 0044
(2019/04/04)
-
- Hydrophosphonylation of Alkynes with Trialkyl Phosphites Catalyzed by Nickel
-
The use of simple and inexpensive NiCl2?6 H2O as a catalyst precursor for C?P bond formation in the presence of commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu, SiMe3) along with several alkynes is presented. Control experiments showed the in situ formation of (RO)2P(O)H as the species that undergo the addition into the C≡C bond at the alkynes to yield the product of P?H addition. The hydrophosphonylation of diphenylacetylene with P(OEt)3, P(OiPr)3, and P(OSiMe3)3 proceeds in high yields (>92 %) without the need of a specific solvent or ligand. This method is useful for the preparation of organophosphonates for both phenylacetylene as a terminal alkyne model and internal alkynes in yields that range from good to modest.
- Islas, Rosa E.,García, Juventino J.
-
p. 4125 - 4131
(2017/10/09)
-
- Preparation method of tris(trimethylsilyl) phosphate
-
The invention discloses a preparation method of tris(trimethylsilyl) phosphate. The preparation method is characterized in that trimethylchlorosilane and inorganic phosphate are added to a reactor provided with a reflux condensation device, the mixture is heated to react, crude tris(trimethylsilyl) phosphate is generated, after the reaction ends, solid-liquid separation is performed, and tris(trimethylsilyl) phosphate is obtained after a liquid-phase product is rectified. According to the method, raw materials are low in price and easy to obtain, reaction conditions are mild, and byproducts are easy to recover.
- -
-
Paragraph 0018; 0019; 0021; 0023; 0025; 0027; 0029
(2018/02/03)
-
- Lifetime limit of tris(trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries
-
The tris(trimethylsilyl) phosphite (TMSPi) is considered as an ideal electrolyte additive for lithium ion batteries. In this work, its positive effect as well as its failure mechanism in a LiPF6 containing electrolyte was studied by means of selected electrochemical, structural and analytical techniques. The LiNi0.5Co0.2Mn0.3O2/graphite cells with TMSPi as electrolyte additive were cycled between 2.8 and 4.6 V. Thanks to the compact cathode electrolyte interphase formed by the oxidative decomposition of TMSPi in a freshly prepared TMSPi containing electrolyte, both the discharge capacity and the cycling stability of cells were enhanced. However, our results also show that TMSPi actually reacts with LiPF6 at room temperature. TMSPi is consumed by this spontaneous reaction after aging for certain time. In addition, a part of the fluorophosphates, generated from the hydrolysis of LiPF6, is bonded to one or two TMS groups, causing a decrease in the fluorophosphate content in the CEI film. Consequently, the cycling stability of the lithium ion cells with aged TMSPi containing electrolyte deteriorates. The obtained results offer important insights into the practical application of TMSPi, which means that TMSPi can only be used as an effective additive in a freshly prepared LiPF6 containing electrolyte.
- Qi, Xin,Tao, Liang,Hahn, Hendrik,Schultz, Carola,Gallus, Dennis Roman,Cao, Xia,Nowak, Sascha,R?ser, Stephan,Li, Jie,Cekic-Laskovic, Isidora,Rad, Babak Rezaei,Winter, Martin
-
p. 38342 - 38349
(2016/05/19)
-
- An efficient method for the preparation of silyl esters of diphosphoric, phosphoric, and phosphorous acid
-
Tetrakis(trialkylsilyl) diphosphate (alkyl = Me, Et, iPr, tBu) can be obtained in quantitative yield by reacting commercial disodium dihydrogen diphosphate with the respective trialkyl chlorosilane in a triphasic system with formamide. The alkylsilane residues of the diphosphate silyl esters can be either partially or completely hydrolyzed without concurrent cleavage of the P-O-P bond of the diphosphate moiety. The method can be expanded to efficiently produce other persilylated or partially silylated phosphates and phosphites.
- Wessjohann, Ludger A.,Dessoy, Marco A.
-
p. 133 - 137
(2014/02/14)
-
- Reaction of bis(trimethylsiloxy)phosphine with trimethylsilane
-
Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate and trimethylsilyl [3-(trimethylsilyl)propyl]-phosphinate are obtained by the reaction of bis(trimethylsiloxy)phosphine with trimethylallylsilane and converted into [3-(trimethylsilyl)propyl]phosphinic and [3-(trimethylsilyl) propyl]phosphonic acid, respectively, by the reaction with methanol.
- Voronkov,Pestunovich,Albanov,Kukhareva
-
experimental part
p. 1080 - 1082
(2011/05/04)
-
- Reaction of tris(trimethylsilyl) phosphite with epoxides and glicydol derivatives
-
Tris(trimethylsilyl) phosphite deoxygenates styrene epoxide and tritylglycidol.The same phosphite with glicydyl mesylate gave bis(trimethylsilyl) ester of 3-mesyl-2-trimethylsiloxypropylphosphonic acid by attack at the epoxide methylene carbon.The ester was not stable and reacted further intramolecularly.With glicydyl tosylate and glicydyl 3-nitrobenzenesulfonate, howewer, the reaction was more complicated and glyceryl 1,3-bis(arenosulfonate) was one of the products.With these activated glycidols deoxygenation and reduction of the nitro group were also observed.Key words: Tris(trimethylsilyl) phosphite, tritylglycidol, activated glicidols, phosphonates, Arbuzov reaction.
- Serves, Spyros V.,Sotiropoulos, Demetrios N.,Ioannou, Panayiotis V.
-
-
- Process for the conditioning and/or purification of organic isocyanates
-
The present invention relates to a process for the conditioning and/or purification of organic isocyanates by a) mixing organic isocyanates at 20° to 150° C. with 0.001 to 1 mole %, based on the isocyanate, of a silylated acid corresponding to the formula wherein X represents the neutral acid residue obtained by removing the acidic hydrogen atoms from an n-basic acid having a pKa value of at most 3, with the exception of hydrohalic acids and n is an integer from 1 to 3, and b) optionally working up the resulting mixture by distillation after a residence time of at least 5 minutes.
- -
-
-
- PHOSPHORYLATION OF DISILYLATED CARBOXAMIDES
-
The reaction of phosphorus(III) acid chlorides and dichlorides with disilylated carboxamides leads to the formation of mono- and bis-(trimethylsilyl)phosphites.The reactions of diethyl phosphorochloridate, O,O-diethyl phosphorochloridothioate, methylphosphonic dichloride, and phosphoryl chloride with disilylated acetamide proceed with the replacement of chlorine atoms by trimethylsiloxy groups.It was shown that β breakdown can occur in the P(S)-N=P-OSiMe3.
- Pudovik, M. A.,Kibardina, L. K.,Pudovik, A. N.
-
p. 960 - 964
(2007/10/02)
-
- Preparation and Spectroscopic Properties of Me3SiOP(S)Cl2, Me3SiOP(S)Br2 and ME3SiOP(O)Br2
-
Trimethylsilyl dichlorothiophosphate (Me3SiOP(S)Cl2) and trimethylsilyl dibromothiophosphate (Me3SiOP(S)Br2 are prepared by reactions of (Me3Si)2S with POCl3 and POBr3, respectively.The reaction of POBr3 with Me3SiOCOCH3 in the mol ratio 1:1 gives Me3SiOP(O)Br2, a molar ratio of 1:3 leads to (Me3SiO)3PO.The vibrational spectra have been used to elucidate the structures of the compounds.It was found that -OP(S)Cl2 as well as -OP(S)Br2 are linked to the trimethylsilyl group through the oxygen atom. - Key words: Preparation, Properties, Vibrational Spectra, 31P NMR Spectra
- Shihada, Abdel-Fattah,Majed, Rehab
-
p. 976 - 980
(2007/10/02)
-
