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 reaction of the a-trimethylsiloxy-phosphoryl compounds Ph2C˭C(OSiMe3)P(:O)R2 [R = Me2N, OMe, OPh] with F3B · OEt2 yielded the donor-acceptor-complexes 1-3 by cleavage of the Si‒O bond and elimination of Me3SiF and Et2O. The complexes 4 and 5 were formed analogously by the reaction of Me(Ph)C˭C(OSiMe3)P(:O)R2 [R = Me, Ph] with F3B · OEt2. The reaction of dimethyl- and diphenyl-2-trimethylsiloxy-3,5-di-tert-butylphenyl phosphinate with F3B · OEt2 produced the seven-membered ring-systems 6 and 7. Analogous products, 8-11, were formed by the reaction of (RO)2P(:O)OR1 [R = Me, 1Pr; R1 = 9-(10 trimethylsiloxy)phenanthryl, 2-trimethylsiloxy-3,4,5,6-tetrachlorophenyl] with F3B · OEt2. The reaction of Me2P(:O)C(OSiMe3)(H)CCl3 with F3B · OEt2 produced the 1:1 complex 12 without cleavage of the Si‒O bond. From α-hydroxy phosphine oxides and F3B · OEt2 similarly, the 1:1 complexes, 13 and 14, were formed. Diphenyl-2-hydroxy-3,5-di-tert-butylphenyl phosphinate reacted with F3B · OEt2 to give the 1:1 complex 15. The structure of 15 was confirmed by X-ray structure analysis; the bond lengths at the bridging oxygen are P-O1 151.7, B-O1 152.8 pm. The donor-acceptorinteraction between the phosphoryl group and the boron atom was established by 19F-,31P- and, in the case of 6, 7, 11, and 15, by 11B-n.m.r-spectroscopy. Key Words: Boron trifluoridephosphoryl groupX-ray structuredonor-acceptor interaction.

Preparation and Structures of Some Intramolecular Donor‐Acceptor Complexes with the Phosphoryl Group as DonorThe reaction of [2,2‐diphenyl‐1‐(trimethylsiloxy)ethenyl]‐dimethylphosphane oxide (1) with PF5 yields 2, involving hexacoordinated phosphorus, by cleavage of the Si–O bond and elimination of (CH3)3SiF. The same compound was formed in the reaction of 1 with RPF4 (R = dimethylamino, morpholino) by cleavage of the P–N bond and elimination of the corresponding silylated amine, R2NSiMe3. The reaction of 1 with F3B · OEt2 led to the intramolecular donor‐acceptor‐complex 3 with a tetracoordinated boron atom. The complex 4 with penta‐ (or hexa)coordinated tin was prepared by reaction of 1 with tin(IV) chloride with elimination of (CH3)3SiCl. X‐ray structure analyses of 2 and 3 confirm the donor‐acceptor interaction between the oxygen atom of the PO group and the PF4 or BF2 group.

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 reaction of the alpha-trimethylsiloxy-phosphoryl compounds Ph2C=C(OSiMe3)P(:O)R2 [R = Me2N, OMe, OPh] with F3B.OEt2 yielded the donor-acceptor-complexes 1-3 by cleavage of the Si-O bond and elimination of Me3SiF and Et2O. The complexes 4 and 5 were formed analogously by the reaction of Me(Ph)C=C(OSiMe3)P(:O)R2 [R = Me, Ph] with F3B.OEt2. The reaction of dimethyl- and diphenyl-2-trimethylsiloxy-3,5-di-tert-butylphenyl phosphinate with F3B.OEt2 produced the seven-membered ring-systems 6 and 7. Analogous products, 8-11, were formed by the reaction of (RO)2P(:O)OR1 [R = Me, (i)Pr; R1 = 9-(10-trimethylsiloxy)phenanthryl, 2-trimethylsiloxy-3,4,5,6-tetrachlorophenyl] with F3B.OEt2. The reaction of Me2P(:O)C(OSiMe3)(H)CCl3 with F3B.OEt2 produced the 1:1 complex 12 without cleavage of the Si-O bond. From alpha-hydroxy phosphine oxides and F3B.OEt2 similarly, the 1:1 complexes, 13 and 14, were formed. Diphenyl-2-hydroxy-3,5-di-tert-butylphenyl phosphinate reacted with F3B.OEt2 to give the 1:1 complex 15. The structure of 15 was confirmed by X-ray structure analysis; the bond lengths at the bridging oxygen are P-O1 151.7, B-O1 152.8 pm. The donor-acceptor-interaction between the phosphoryl group and the boron atom was established by F-18, P-31 and, in the case of 6, 7, 11, and 15, by B-11-n.m.r-spectroscopy.

The reactions of the acids la-4a and 8a with 1,3,5-trimethylhexahydro-1,3,5-triazine furnished compounds 1b-4b and 8b. The IR investigation of 1 b, 4b and 8b revealed P=O ··· H—N interactions. In the unusual reaction of lb with methyl iodide the quaternary ammonium iodide [(H 3 C) 2 P(:O)CH 2 N(CH 3 ) 3 ]+I- 1c was formed. The reaction of 2b with methyl iodide produced the ammonium iodide [(H 3 C) 2 P(:S)CH 2 NH 2 CH 3 ] + I- 2c. The structure of 2c was confirmed by X-ray crystal structure analysis, which showed the expected distorted tetrahedral geometry at phosphorus and revealed N—H ••• I hydrogen bonds. Reaction of 8b with methyl iodide led to the formation of the ammonium iodide 8c by methylation at the nitrogen atom. In the reaction of lb and 2b with HPF 6 the compounds 1 d and 2d were obtained. The compounds 1 d and 2d, due to their instability at room temperature, could be identified only by 1 H and 31 P NMR spectroscopy.

The reactions of the acids 1a-4a and 8a with 1,3,5-trimethylhexahydro-1,3,5-triazine furnished compounds 1b-4b and 8b. The IR investigation of 1b, 4b and 8b revealed P=O...H-N interactions. In the unusual reaction of 1b with methyl iodide the quaternary ammonium iodide [(H3C)2P(:O)CH2N(CH3)3]+I- 1c was formed. The reaction of 2b with methyl iodide produced the ammonium iodide [(H3C)2P(:S)CH2NH2CH3]+I- 2c. The structure of 2c was confirmed by X-ray crystal structure analysis, which showed the expected distorted tetrahedral geometry at phosphorus and revealed N-H...I hydrogen bonds. Reaction of 8b with methyl iodide led to the formation of the ammonium iodide 8c by methylation at the nitrogen atom. In the reaction of 1b and 2b with HPF6 the compounds 1d and 2d were obtained. The compounds 1d and 2d, due to their instability at room temperature, could be identified only by H-1 and P-31 NMR spectroscopy.

The reaction of Me2P(:X)H [X = O: 1; X = S: 2] with fluorinated ketones produced the alpha-hydroxyphosphine oxides and sulfides, 3, 4 and 6. The reaction of Me2P(:O)CH2OH with formaldehyde gave the hemiacetal 7. Compound 2 reacted with formaldehyde and chloral to the corresponding alpha-hydroxyphosphine sulfides, 8 and 9. The reaction of 2 with glyoxal furnished the 2:1 addition product 10. In the case of diacetyl and benzil, the 1:1 addition products 12 and 12 were formed. The reaction of 2 with acetone and cyclohexanone produced in the same fashion 13 and 14. The reaction of 2 with pivaloyl chloride was found to occur with formation of the diphosphine monosulfide 15. In the case of benzoyl chloride, the 2:1 addition-product 16 was formed. Compound 1 reacted with diketene with formation of the alpha-hydroxy-bis(phosphine oxide) 17. The reaction of selected alpha-hydroxy-phosphine oxides and sulfides with different trimethylsilylating reagents produced the corresponding trimethylsilylated compounds, 18-23.

The reaction of R2POSiMe3 [R = Me, Ph, Me2N, O(i)Pr] with 3,5-di-tert-butyl-o-benzoquinone led to the 2-trimethylsiloxyphenyl phosphoric derivatives 1-4. In the case of the trimethylsilylphosphites (RO)2POSiMe3 [R = Me, Et, Ph], the benzo-1,3,2-dioxaphospholines 5-7 were formed by elimination of the corresponding silylethers ROSiMe3. The reaction of R2POSiMe3 [R = Me, Me2N, OMe, O(i)Pr, OPh] with tetrachloro-o-benzoquinone produced the 2-trimethylsiloxyphenyl-phosphoric acid esters and esteramides 8-12. The same type of reaction was established between R2POSiMe3 [R = Me, Et2N, OMe, O(i)Pr, OPh] with 9,10-phenanthrenequinone which produced compounds 13-17. The structure of compound 16 was confirmed by a single crystal X-ray analysis. The reaction of the phosphine oxides R2P(:O)H [R = Me, Ph] with 3,5-di-tert-butyl-o-benzoquinone was found to furnish the catechol phosphinic acid esters 18 and 19. The diorganophosphites (RO)2P(:O)H [R = Me, O(i)Pr, Ph] reacted with tetrachloro-o-benzoquinone in the same fashion to give the catechol phosphoric acid esters, 20-22.

The reaction of R2POSiMe3 [R = Ph, Me2N, OMe, OEt, O(i)Pr, OPh] with diphenylketene was found to occur with 1,4-trimethylsilyl migration and formation of the corresponding silylated compounds, 1-6. Hydrolysis of compound 1 gave the hydroxy-compound 7. The reaction of tBuPhPOSiMe3 with diphenylketene produced the racemic alpha-silylated phosphine oxide 8. The reaction of tBuPhPOSiMe3 with trimethylsilyl azide led to compound 9. According to NMR studies (H-1, C-13, P-31), 9 was present as a phosphine imide. The reaction of R2POSiMe3 [R = Me, Ph, Me2N, OPh] with the unsymmetric methylphenylketene produced the silylated compounds 10-13. H-1-nmr-studies showed the stereospecific formation of the Z-isomers.

The reaction of naphthalene-2,3-diol 1 with PCl3 was found to furnish the hydridophosphorane 3, with PCl5 the chlorophosphorane 4 was formed. The reaction of the fluorophosphoranes, RPF4 [R=F, (i)Pr, CH2SiMe3, CH2Cl, Ph] with the bis(trimethylsilyl) derivative of 1, 2 yielded the corresponding spirocyclic phosphoranes, 5-9 by cleavage of the Si-O bond and elimination of Me3SiF. The difluorophosphoranes, R2PF3 [R=Me, Ph] reacted with 2 to form the monocyclic phosphoranes, 10 and 11, where the fluorine atom occupies an axial position at trigonal-bipyramidal (TBP) phosphorus- The structure of compound 11 was confirmed by single crystal X-ray analysis of its dichloromethane hemisolvate at -95-degrees-C. The geometry at phosphorus is trigonal-bipyramidal. whereby the naphthalenedioxy ligand spans an axial and an equatorial site. Me2PF3 reacted with tetrakis(1,2,4.5-trimethylsiloxy)benzene to form the bifunctional benzodioxa-lambda5-phosphole, 12.

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.

Reactions of Fluorophosphoranes with Trimethylsilyl (Trimethylsilyloxy)acetate: Structures, NMR‐Spectroscopic Studies and X‐ray Investigations of Mono‐ and Spirocyclic (Acyloxy)phosphoranes[1]The reaction of the tetrafluorophosphoranes RPF4 (R = Me, Ph) with trimethylsilyl (trimethylsilyloxy)acetate (1) yields the corresponding monocyclic fluoro(acyloxy)phosphoranes 2 and 3 by cleavage of the Si—O bond and elimination of (CH3)3SiF. 2 and 3 were investigated by NMR spectrometry. The spirocyclic (acyloxy)phosphoranes 4–13 are formed analogously by the reaction of 1 with the fluorophosphoranes RPF4 [R = F, Me, Et, iPr, Me3SiCH2, CH2Cl, CHCl2, H2C = CH, C6H5, 2,5‐(CH3)2C6H3] in a molar ratio of 2:1. Spirophosphorane 14 is synthesized by the reaction of with PhN3 in the presence of a base. The trifluorophosphoranes R2PF3 (R = Me, Ph) react with 1 to form the monocyclic fluoro(acyloxy)phosphoranes 15 and 16, where the fluorine atom occupies an axial position at trigonal‐bipyramidal (TBP) phosphorus. X‐ray structure analyses of 4 and 7 reveal TBP geometry at phosphorus. The acyloxy ligand is found to form a chelate ring, whereby one axial and one equatorial site at TBP phosphorus are bridged.

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 reaction of the N-trimethylsilyl-substituted heterocycles. trimethylsilyl-pyrazole. 1, -imidazole. 3, -5.6-dimethylbenzimidazole, 7. and 1.3.4-triazole. 8 with phosphorus pentafluoride was studied. The reaction proceeded via the initial formation of 1:1 Lewis acid-base adducts between phosphorus pentafluoride and the nitrogen atom bearing the Me3Si group. In the reaction of 1 with PF5 the unusual bis-tetrafluorophosphate complex. 2 was directly formed by cleavage of Si-N bonds and elimination of Me3SiF. The reaction of the trimethylsilylated triazole. 8 with PF5 produced a mixture of substances. The dimer 5 was formed during thermolysis of 4. The products were characterized by 1H, 13C, 19F and 31P n.m.r spectroscopy. A single crystal X-ray structure detemination was conducted for the pyrazole-bridged bis-tetrafluorophosphate complex. 2. in which the central six-membered ring (P2N4) adopts a boat conformation.

AbstractThe reaction of (I) with the dienes (II), (IV), (VI) and (VIII) is found to occur with 1,3‐trimethylsilyl migration yielding the corresponding derivatives (III), (V) and (VII).