二氯硅烯与乙烯和甲醛环加成反应机理的理论研究

用RHF/6-31G^*解析梯度方法研究了单重态二氯硅烯与乙烯和甲醛环加成反应的机理,并用二级微扰方法对各构型能量进行了相关能校正.结果表明,两反应历程均由两步组成:(1)二氯硅烯与乙烯和甲醛分别生成了中间配合物,是无势垒的放热反应;(2)中间配合物异构化成产物二氯硅杂环丙烷和二氯硅杂环氧甲烷,其势垒经零点能校正分别为97.43和103.29kJ/mol(MP₂/6-31G^*//6-31G^*).     

Synthesis of substituted vinylgermanes and germylsilylethenes via ruthenium complex catalyzed germylation of olefins

A series of substituted vinylgermanes and divinylgermanes have been synthesized in moderate or high yield via two reactions of olefins and dienes catalyzed by [RuHCl(CO) (PCy₃)₂], i.e. germylative coupling with vinylgermanes and dehydrogenative germylation with hydrogermanes. While the former reaction can be a versatile way of regioselective synthesis of products (particularly useful for the stereoselective synthesis of germylsilylethenes), the latter could be used as a complement, especially in synthesis of germylate dioxol ethene and vinyl ethers. Copyright © 2008 John Wiley & Sons, Ltd.     

Valence Isomerization of a 1,3-Diphosphacyclobutane-2,4-diyl: Photochemical Ring Closure to 2,4-diphosphabicyclo[1.1.0]butane and Its Thermal Ring Opening to gauche-1,4-Diphosphabutadiene

The bond stretch isomer 1,3-diphosphacyclobutane-2,4-diyl 1 was transformed photochemically to give the previously unknown 2,4-diphosphabicyclo[1.1.0]butane 2 , which itself can be converted thermally into gauche-1,4-diphosphabutadiene 3 . The crystal structures of these three energy-rich valence isomers of 1,2-diphosphete have been determined. R=SiMe₃; Mes*=2,4,6-tBu₃C₆H₂.     

Reactive E=C(p‐p)π‐Systems. 56 [1] Attempted Preparation of PhE=C(CF3)2 by Reactions of Hexafluoroacetone with PhE(SiMe3)2 (E = As,P)

The chance to prepare sterically and inductively stabilized arsa‐ and phosphaalkenes of the type PhE=C(CF₃)₂ (E = As, P) by reacting phenyl‐bis(trimethylsilyl)‐arsane ( 1 ) and ‐phosphane ( 5 ), respectively, with hexafluoroacetone (HFA) was investigated. The insertion of the carbonyl function in one of the Si–E bonds was found to occur at temperatures between ?78 and 20 °C. The elimination of hexamethyldisiloxane, which in case of acylamides and ketones spontaneously follows the insertion and in case of RE(SiMe₃)–CR′₂(OSiMe₃) at least can be initiated by solid sodium hydroxide as catalyst, turned out to be impossible for the primary products PhE(SiMe₃)–C(CF₃)₂‐OSiMe₃ [E = As ( 2 ), P ( 6 )]. 2 and 6 were characterized by analytical (C, H) and spectroscopic methods (IR, NMR, MS).     

Synthese und Molekülstruktur neuer Ringsysteme aus 1,1,3,3-Tetrachlor-1,3-diphosphapropan

Synthesis and Molecular Structure of new Ring Systems from 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1 reacts in two different ways to form new heterocycles. Partial oxidation of 1 with tetrachloroorthobenzoquinone furnishes the methylene-bridged λ³P, λ⁵P species 3 . Subsequent reactions with di- and triethylamine lead to the condensed ring system 6 with the P?C bonds connected to a central four-membered ring. Compound 6 displays crystallographic inversion symmetry, a short transannular P? P distance and an extremely distorted tetrahedral coordination geometry at the four-membered ring phosphorus atoms. 1 reacts with 7 to give the heterocycle 8 with a central eight-membered ring involving four phosphorus atoms. The eight – membered ring shows a ?bent”? crown conformation, the condensed five – membered rings display envelope conformation.     

Preparations and properties of polymers containing 3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]-1,2-di(2-thienyl)cyclobutene moieties

Reaction of 1,8-bis[5-{(2,4,6-tri-t-butylphenyl)phosphinoethynyl}-2-thienyl]octane with butyllithium followed by treatment with 1,2-dibromoethane afforded a new polymer containing 3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]-1,2-di(2-thienyl)cyclobutene units. The polymer was allowed to react with bis(benzonitrile)dichloropalladium to give the polymer complex. A Sonogashira coupling reaction between ethynyltrimethylsilane and 4-bromonitrobenzene proceeded in DMF at 100 °C to give 4-nitro(trimethylsilylethynyl)benzene in the presence of the polymer complex, CuI, and triethylamine.     

Facile [3+2] dimerization and formal dehydrogenative coupling mode of a cyanophenylphosphaallene

Due to a facile head-to-tail [3+2] dimerization, even a sterically demanding group such as the Mes^∗ (2,4,6-tri-tert-butylphenyl) group around the PCC moiety did not allow us to isolate 3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene from the elimination reaction of 2-bromo-3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaprop-1-ene with DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and the corresponding 1,4-diphosphafulvene containing cyano groups was obtained and characterized. Theoretical studies on the [3+2] dimerization of phosphaallene characterize possible intermediates affording 1,4-diphosphafulvenes and also suggest the cyano group effect to facilitate the saturation of the PC double bonds. On the other hand, 1,2-bis(4-cyanophenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene was obtained from 2-bromo-3-(4-cyanophenyl)-3-trimethylsiloxy-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaprop-1-ene together with the 3-(4-cyanophenyl)-1-phosphaallene.     

Zur Reaktivität des Ferriophosphaalkens (Z)‐[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C‐CO2R (R=Me,Et) und Acetylendicarbonsäureestern RO2C‐C≡C‐CO2R (R=Me,Et, tBu)

On the Reactivity of the Ferriophosphaalkene (Z)‐[Cp*(CO)₂Fe‐P=C(tBu)NMe₂] towards Propiolates HC≡C‐CO₂R (R=Me, Et) and Acetylene Dicarboxylates RO ₂C‐C≡C‐CO₂R (R=Me, Et, tBu) The reaction of equimolar amounts of (Z)‐[Cp*(CO)₂Fe‐P=C(tBu)NMe₂] 3 and methyl‐ and ethyl‐propiolate ( 2a, b ) or of 3 and dialkyl acetylene dicarboxylates 1a (R=Me), 1b (Et), 1c (tBu) afforded the five‐membered metallaheterocycles [Cp*(CO) =C(tBu)NMe₂] ( 4a, b ) and [Cp*(CO) =C(tBu)NMe₂] ( 5a—c ). The molecular structures of 4b and 5a were elucidated by single crystal X‐ray analyses. Moreover, the reactivity of 4b towards ethereal HBF₄ was investigated.     

Synthesis of Mixed-Functionalized Tetraacylgermanes

Tetraacylgermanes are known as highly efficient photoinitiators. Herein, the synthesis of mixed tetraacylgermanes 4 a – c and 6 a – e with a nonsymmetric substitution pattern is presented. Germenolates are crucial intermediates of these new synthetic protocols. The synthesized compounds show increased solubility compared with symmetrically substituted tetraacylgermanes 1 a – d . Moreover, these mixed derivatives reveal broadened n–π* absorption bands, which enhance their photoactivity. Higher absorption of these new compounds at wavelengths above 450 nm causes efficient photobleaching when using an LED emitting at 470 nm. The quantum yields are in the range of 0.15–0.57, depending on the nature of the aroyl substituents. On the basis of these properties, mixed-functionalized tetraacylgermanes serve as ideal photoinitiators in various applications, especially in those requiring high penetration depth. The synthesized compounds were characterized by elemental analysis, IR spectroscopy, NMR and CIDNP spectroscopy, UV/Vis spectroscopy, photolysis experiments, and X-ray crystallography. The CIDNP data suggest that the germyl radicals generated from the new tetraacylgermanes preferentially add to the tail of the monomer butyl acrylate. In the case of 6 a – e only the mesitoyl groups are cleaved off, whereas for 4 a – c both the mesitoyl and the aroyl group are subject to α-cleavage.     

Alternative Synthesis and Structures of C‐monoacetylenic Phosphaalkenes

An alternative synthesis of C‐monoacetylenic phosphaalkenes trans‐Mes*P=C(Me)(C≡CR) (Mes* = 2, 4, 6‐^tBu₃Ph, R = Ph, SiMe₃) from C‐bromophosphaalkenes cis‐Mes*P=C(Me)Br using standard Sonogashira coupling conditions is described. Crystallographic studies confirm cis‐trans isomerization of the P=C double bond during Pd‐catalyzed cross coupling, leading exclusively to trans‐acetylenic phosphaalkenes. Crystallographic studies of all synthesized compounds reveal the extend of π‐conjugation over the acetylene and P=C π‐systems.     

Metallophosphaalkenes—from Exotics to Versatile Building Blocks in Preparative Chemistry

The chemistry of low-valent organophosphorus compounds such as phosphaalkenes and phosphaalkynes has undergone rapid development in the last two decades. This development also includes the coordination chemistry of these species, which can act as versatile ligands in metal complexes. Metallophosphaalkenes are compounds in which one or more of the organic substituents on the P?C unit is replaced by a transition metal complex fragment. Metallophosphaalkenes have emerged from an existence as laboratory curiosities to become a link between main group and organometallic complex chemistry. The great richness of their chemistry not only mirrors the specific properties of the individual building block, but also shows novel and individual traits. Particular examples are cycloadditions of these electron-rich heteroalkenes with electron-deficient alkenes, alkynes, azo, and diazo compounds. These often lead to novel types of reaction and compounds. Metallophosphaalkenes are also important as intermediates in all metal-assisted cyclooligomerizations of phosphaalkynes.     

Reactivity of Phosphaalkenes toward Carbene Complexes

Reaction of phosphaalkenes RP=C(NMe 2 ) 2 (R = t -Bu, Me 3 Si), featuring an inverse distribution of electron density about the P--C double bond, with Fischer carbene complexes [(CO) 5 M=C(OEt)Ar] (Ar=Ph, 2-MeC 6 H 4 , 2-MeOC 6 H 4 , M = Cr, W) afforded a mixture of complexes [(CO) 5 M{P(R)=C(NMe 2 ) 2 }] and [(CO) 5 M{P(R)=C(OEt)Ar}]. The treatment of phosphaalkene HP=C(NMe 2 ) 2 with compound [(CO) 5 W=C(OEt)(2-MeOC 6 H 4 )] gives rise to the formation of an ( E / Z )-mixture of [(CO) 5 W{P(CH(NMe 2 ) 2 )=C(OEt)(2-MeOC 6 H 4 )}].     

Zur Reaktivität der Ferriophosphaalkene [(η5‐C5Me5)(CO)2FeP=C(NR)R2] (NR = NMe2, NC5H10, R2 = Ph,tBu) gegenüber Protonsäuren,Alkylierungsmitteln und [{(Z)‐Cycloocten}Cr(CO)5]

Transition Metal‐substituted Phosphaalkenes. 42 Reactivity of the Ferriophosphaalkenes [(η⁵‐C₅Me₅)(CO)₂FeP=C(NR )R²] (NR = NMe₂, NC₅H₁₀, R² = Ph, t Bu) towards Protic Acids, Alkylation Reagents, and [{( Z )‐Cyclooctene}Cr(CO)₅] The reaction of equimolar amounts of [(η⁵‐C₅Me₅)(CO)₂FeP=C(NR )R²] ( 2 a : NR = NMe₂, R² = Ph; 2 b : NMe₂. tBu; 2 c : NC₅H₁₀, Ph) and etherial HBF₄ gave rise to the formation of [(η⁵‐C₅Me₅)(CO)₂FeP(H)C(NR )R²] (BF₄) ( 3 a – c ) which were isolated as light red powders. Compounds 2 a – c were converted into [(η⁵‐C₅Me₅)(CO)₂FeP(Me)C(NR )R²] (SO₃CF₃) ( 4 a – c ) by treatment with methyl trifluoromethane sulfonate. In addition 2 a and Me₃SiCH₂OSO₂CF₃ afforded light red [(η⁵‐C₅Me₅)(CO)₂FeP(CH₂SiMe₃)C(NMe₂)Ph](SO₃CF₃) ( 5 ). The black complex [(η⁵‐C₅Me₅)(CO)₂FeP{Cr(CO)₅}C(NMe₂)Ph] ( 6 ) resulted from the combination of 2 a with [{(Z)‐cyclooctene}Cr(CO)₅]. The novel products were characterized by elemental analyses and spectra (IR, ¹H‐, ¹³C‐ und ³¹P‐NMR).     

Visible-Light-Triggered Photoswitching of Diphosphene Complexes

Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [( 2 -κ²P,κ⁶C)Mo(CO)₂][OTf] ( 3 a [OTf]), [( 2 -κ²P,κ⁶C)Fe(CO)][OTf] ( 3 b [OTf]), and [( 2 -κ²P)Fe(CO)₄][OTf] ( 4 [OTf]) were prepared using the triflate salt [(L_C)P=P(Dipp)][OTf] ( 2 [OTf) as a precursor (L_C=4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate). Upon exposure to blue or UV light (λ=400 nm, 470 nm), the initially red-colored η²-diphosphene complexes 3 a , b [OTf] readily undergo isomerization to form blue-colored η¹-complexes [( 2 -κ¹P,κ⁶C)M(CO)_n][OTf] ( 5 a , b [OTf]; a : M=Mo, n=2; b : M=Fe, n=1). This haptotropic rearrangement is reversible, and the (κ²P,κ⁶C)-coordination mode gradually reverts back upon dissolution in coordinating solvents or more rapidly upon exposure to yellow or red irradiation (λ=590 nm, 630 nm). The electronic reasons for the reversible visible-light-induced photoswitching observed for 3 a , b [OTf] are elucidated by DFT calculations. These calculations indicate that the photochromic isomerization originates from the S₁ excited state and proceeds through a conical intersection.     

Synthesis of Tris(pentafluoroethyl)germanes

The synthesis of tris(pentafluoroethyl)germanium derivatives is described. The reaction of germanium tetrachloride with three equivalents of the pentafluoroethylation reagent LiC₂F₅ does not lead selectively to the formation of tris(pentafluoroethyl)chlorogermane, (C₂F₅)₃GeCl. Here the introduction of a diethylamino function as a protecting group was beneficial. Thus, treatment of Cl₃GeNEt₂ with LiC₂F₅ smoothly afforded (C₂F₅)₃GeNEt₂. The replacement of the amino substituent by halides was accomplished by reaction with HBr or HCl on a multigram scale. The combination of (C₂F₅)₃GeCl with Ag₂CO₃ gave rise to the formation of the digermoxane [(C₂F₅)₃Ge]₂O. An obtuse Ge‐O‐Ge angle of 150.2(1)° was determined by X‐ray diffraction. Attempted hydrolysis of the digermoxane leads to an equilibrium mixture of the precursor, (C₂F₅)₃GeOH, and water.     

Azodicarbonsäureester und Diazoessigester als Reaktionspartner des Ferriophosphaalkens [Cp*(CO)2FeP=C(Ph)NMe2]

Azodicarboxylates and Diazoacetates as Reactants of the Ferriophosphaalkene [Cp*(CO)₂FeP=C(Ph)NMe₂] Reaction of equimolar amounts of the ferriophosphaalkene [Cp*(CO)₂FeP=C(Ph)NMe₂] ( 1 ) and diethyl azodicarboxylate afforded the complex (C₅Me₄CH₂)(CO)₂Fe ( 3 ) as the result of a cheletropic [1+4] cycloaddition with subsequent transprotonation. The diazoacetates N₂=CHCO₂R ( 8a :=tBu; 8b :Et) and 1 gave rise to the formation of the N‐metallated 1, 2, 3‐diazaphospholes [Cp*(CO)₂Fe‐ ] ( 11a, b ). Compounds 3, 11a and 11b were characterized by means of elemental analyses and spectroscopy (IR, ¹H, ¹³C{¹H}, ³¹P{¹H}‐NMR). The molecular structure of 11a was determined by X‐ray diffraction analysis.