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1.
Christian Marquardt Dr. Christine Thoms Andreas Stauber Dr. Gábor Balázs Dr. Michael Bodensteiner Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2014,53(14):3727-3730
Whilst catena‐phosphorus cations have been intensively studied in the last years, mixed Group 13/15 element cationic chains have not yet been reported. Reaction of the pnictogenboranes H2EBH2?NMe3 (E=P, As) with monohalideboranes lead to the cationic chain compounds [Me3N?BH2EH2BH2?NMe3][X] (E=P, As; X=AlCl4, I) and [Me3N?BH2PH2BH2PH2BH2?NMe3][X] (X=I, VCl4(thf)2), respectively. All of the compounds have been characterized by X‐ray structure analysis, NMR spectroscopy, IR spectroscopy, and mass spectrometry. DFT calculations elucidate the reaction pathway, the high thermodynamic stability, the charge distribution within the chain and confirm the observed solid‐state structures. 相似文献
2.
Clemens Taube Dr. Kai Schwedtmann Medena Noikham Prof. Dr. Ekasith Somsook Dr. Felix Hennersdorf Prof. Dr. Robert Wolf Prof. Dr. Jan J. Weigand 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(9):3613-3619
[LCRP((PhP)2C2H4)][OTf] ( 4 a,b [OTf]) and [LCiPrP(PPh2)2][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [LCRP(pyr)2][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; LCR=1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P−N/P−P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph2P)2(LCMeP)2][OTf]2 ( 7 a [OTf]2) is observed when reacting 3 a [OTf] with diphosphane P2Ph4. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH3CN)4]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLCiPr)Au}4][OTf]4 ( 9 [OTf]4) was unexpectedly formed as a result of a chloride-induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH3CN)3][OTf]2 (M=Cu, Ag) ( 10 [OTf]2, 11 [OTf]2). 相似文献
3.
Clemens Taube Kai Schwedtmann Medena Noikham Ekasith Somsook Felix Hennersdorf Robert Wolf Jan J. Weigand 《Angewandte Chemie (International ed. in English)》2020,59(9):3585-3591
[LCRP((PhP)2C2H4)][OTf] ( 4 a,b [OTf]) and [LCiPrP(PPh2)2][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [LCRP(pyr)2][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; LCR=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P?N/P?P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph2P)2(LCMeP)2][OTf]2 ( 7 a [OTf]2) is observed when reacting 3 a [OTf] with diphosphane P2Ph4. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH3CN)4]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLCiPr)Au}4][OTf]4 ( 9 [OTf]4) was unexpectedly formed as a result of a chloride‐induced P?P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH3CN)3][OTf]2 (M=Cu, Ag) ( 10 [OTf]2, 11 [OTf]2). 相似文献
4.
Charge Effects in PCP Pincer Complexes of NiII bearing Phosphinite and Imidazol(i)ophosphine Coordinating Jaws: From Synthesis to Catalysis through Bonding Analysis
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Dr. Boris Vabre Dr. Yves Canac Dr. Christine Lepetit Dr. Carine Duhayon Prof. Remi Chauvin Prof. Davit Zargarian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17403-17414
This contribution reports on a new family of NiII pincer complexes featuring phosphinite and functional imidazolyl arms. The proligands RPIMCHOPR′ react at room temperature with NiII precursors to give the corresponding complexes [(RPIMCOPR′)NiBr], where RPIMCOPR=κP,κC,κP‐{2‐(R′2PO),6‐(R2PC3H2N2)C6H3}, R=iPr, R′=iPr ( 3 b , 84 %) or Ph ( 3 c , 45 %). Selective N‐methylation of the imidazole imine moiety in 3 b by MeOTf (OTf=OSO2CF3) gave the corresponding imidazoliophosphine [(iPrPIMIOCOPiPr)NiBr][OTf], 4 b , in 89 % yield (iPrPIMIOCOPiPr=κP,κC,κP‐{2‐(iPr2PO),6‐(iPr2PC4H5N2)C6H3}). Treating 4 b with NaOEt led to the NHC derivative [(NHCCOPiPr)NiBr], 5 b , in 47 % yield (NHCCOPiPr=κP,κC,κC‐{2‐(iPr2PO),6‐(C4H5N2)C6H3)}). The bromo derivatives 3–5 were then treated with AgOTf in acetonitrile to give the corresponding cationic species [(RPIMCOPR)Ni(MeCN)][OTf] [R=Ph, 6 a (89 %) or iPr, 6 b (90 %)], [(RPIMIOCOPR)Ni(MeCN)][OTf]2 [R=Ph, 7 a (79 %) or iPr, 7 b (88 %)], and [(NHCCOPR)Ni(MeCN)][OTf] [R=Ph, 8 a (85 %) or iPr, 8 b (84 %)]. All new complexes have been characterized by NMR and IR spectroscopy, whereas 3 b , 3 c , 5 b , 6 b , and 8 a were also subjected to X‐ray diffraction studies. The acetonitrile adducts 6 – 8 were further studied by using various theoretical analysis tools. In the presence of excess nitrile and amine, the cationic acetonitrile adducts 6 – 8 catalyze hydroamination of nitriles to give unsymmetrical amidines with catalytic turnover numbers of up to 95. 相似文献
5.
《Angewandte Chemie (International ed. in English)》2017,56(41):12783-12787
We report on the synthesis and characterization of mixed pnictogenylboranes. The substitution of the Lewis base SMe2 in (OC)5W–PH2BH2–SMe2 ( 2 ) by different pnictogenylboranes ER2BH2–LB (E=P, As, Sb) leads to the Lewis acid/base stabilized butane analogue (OC)5W–PH2BH2ER2BH2–LB ( 3 a , b : E=P; R=H, SiMe3; LB=NMe3; 4 a , b : E=As; R=H, SiMe3; LB=NMe3; 5 : E=Sb; R=SiMe3; LB=NHCMe). All of these compounds were characterized by single‐crystal X‐ray structure analysis, mass spectrometry, NMR, and IR spectroscopy. In addition, the very unstable phosphanylborane chain PH2BH2PH2BH2–NMe3 ( 1 ) was synthesized. DFT calculations provide insight into the thermodynamics of these reactions. 相似文献
6.
Dieter Enders Ren Peters Ren Lochtman Gerhard Raabe 《Angewandte Chemie (International ed. in English)》1999,38(16):2421-2423
A stereogenic center at the position β to the metallocene backbone is present in ferrocenyl ligands 2 , which are interesting for asymmetric catalysis. These planar-chiral compounds are accessible for the first time by a highly diastereoselective and enantioselective synthesis (de=93–97 %; ee≥96 %) from the ferrocenyl ketones 1 . A variety of donor groups (E1=Ph2P⋅BH3, SMe, SiPr; E2=SMe, STol, SePh, Ph2P⋅BH3, iPr2P⋅BH3) can be introduced as electrophiles. Tol=tolyl=CH3C6H4. 相似文献
7.
Metal‐Free Addition/Head‐to‐Tail Polymerization of Transient Phosphinoboranes,RPH‐BH2: A Route to Poly(alkylphosphinoboranes)
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Christian Marquardt Dr. Titel Jurca Dr. Karl‐Christian Schwan Dr. Andreas Stauber Dr. Alexander V. Virovets Dr. George R. Whittell Prof. Dr. Ian Manners Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2015,54(46):13782-13786
Mild thermolysis of Lewis base stabilized phosphinoborane monomers R1R2P? BH2?NMe3 (R1,R2=H, Ph, or tBu/H) at room temperature to 100 °C provides a convenient new route to oligo‐ and polyphosphinoboranes [R1R2P‐BH2]n. The polymerization appears to proceed via the addition/head‐to‐tail polymerization of short‐lived free phosphinoborane monomers, R1R2P‐BH2. This method offers access to high molar mass materials, as exemplified by poly(tert‐butylphosphinoborane), that are currently inaccessible using other routes (e.g. catalytic dehydrocoupling). 相似文献
8.
Michael A. K. Weinhart Anna S. Lisovenko Alexey Y. Timoshkin Manfred Scheer 《Angewandte Chemie (International ed. in English)》2020,59(14):5541-5545
The synthesis and characterization of the first parent phosphanylalane and phosphanylgallane stabilized only by a Lewis base (LB) are reported. The corresponding substituted compounds, such as IDipp?GaH2PCy2 ( 1 ) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene) were obtained by the reaction of LiPCy2 with IDipp?GaH2Cl. However, the LB‐stabilized parent compounds IDipp?GaH2PH2 ( 3 ) and IDipp?AlH2PH2 ( 4 ) were prepared via a salt metathesis of LiPH2?DME with IDipp?E′H2Cl (E′=Ga, Al) or by H2‐elimination reactions of IDipp?E′H3 (E′=Ga, Al) and PH3, respectively. The compounds could be isolated as crystalline solids and completely characterized. Supporting DFT computations gave insight into the reaction pathways as well as into the stability of these compounds with respect to their decomposition behavior. 相似文献
9.
《Journal of organometallic chemistry》2003,665(1-2):226-232
Photolysis of a benzene solution containing [Fe3(CO)9(μ3-E)2] (E=S, Se), [(η5-C5R5)Fe(CO)2(CCRI)] (R=H, Me; RI=Ph, Fc), H2O and Et3N results in formation of new metal clusters [(η5-C5R5)Fe3(CO)6(μ3-E)(μ3-ECCH2RI)] (R=H, RI=Ph, E=S 1 or Se 2; R=Me, RI=Ph, E=S 3 or Se 4; R=H, RI=Fc, E=S 5; R=Me, RI=Fc, E=S 6 or Se 7). Reaction of [Fe3(CO)9(μ3-S)2]with [(η5-C5R5)Mo(CO)3(CCPh)] (R=H, Me), under same conditions, produces mixed-metal clusters [(η5-C5R5)MoFe2(CO)6(μ3-S)(μ-SCCH2Ph)] (R=H 8; R=Me 9). Compounds 1–9 have been characterised by IR and 1H and 13C-NMR spectroscopy. Structures of 1, 5 and 9 have been established crystallographically. A common feature in all these products is the formation of new C-chalcogen bond to give rise to a (ECCH2RI) ligand. 相似文献
10.
Vincenzo G Albano Fabio Marchetti Stefano Zacchini 《Journal of organometallic chemistry》2004,689(3):528-538
Terminal alkynes (HCCR′) (R′=COOMe, CH2OH) insert into the metal-carbyne bond of the diiron complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(NCMe)(Cp)2][SO3CF3] (R=Xyl, 1a; CH2Ph, 1b; Me, 1c; Xyl=2,6-Me2C6H3), affording the corresponding μ-vinyliminium complexes [Fe2{μ-σ:η3-C(R′)CHCN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Xyl, R′=COOMe, 2; R=CH2Ph, R′=COOMe, 3; R=Me, R′=COOMe, 4; R=Xyl, R′=CH2OH, 5; R=Me, R′=CH2OH, 6). The insertion is regiospecific and C-C bond formation selectively occurs between the carbyne carbon and the CH moiety of the alkyne. Disubstituted alkynes (R′CCR′) also insert into the metal-carbyne bond leading to the formation of [Fe2{μ-σ:η3-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R′=Me, R=Xyl, 8; R′=Et, R=Xyl, 9; R′=COOMe, R=Xyl, 10; R′=COOMe, R=CH2Ph, 11; R′=COOMe, R=Me, 12). Complexes 2, 3, 5, 8, 9 and 11, in which the iminium nitrogen is unsymmetrically substituted, give rise to E and/or Z isomers. When iminium substituents are Me and Xyl, the NMR and structural investigations (X-ray structure analysis of 2 and 8) indicate that complexes obtained from terminal alkynes preferentially adopt the E configuration, whereas those derived from internal alkynes are exclusively Z. In complexes 8 and 9, trans and cis isomers have been observed, by NMR spectroscopy, and the structures of trans-8 and cis-8 have been determined by X-ray diffraction studies. Trans to cis isomerization occurs upon heating in THF at reflux temperature. In contrast to the case of HCCR′, the insertion of 2-hexyne is not regiospecific: both [Fe2{μ-σ:η3-C(CH2CH2CH3)C(Me)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Xyl, 13; R=Me, 15) and [Fe2{μ-σ:η3-C(Me)C(CH2CH2CH3)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Xyl, 14, R=Me, 16) are obtained and these compounds are present in solution as a mixture of cis and trans isomers, with predominance of the former. 相似文献
11.
Dr. Carina Vidovič Prof. Dr. Ferdinand Belaj Prof. Dr. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(54):12431-12444
A series of WIV alkyne complexes with the sulfur-rich ligand hydridotris(2-mercapto-1-methylimidazolyl) borate) (TmMe) are presented as bio-inspired models to elucidate the mechanism of the tungstoenzyme acetylene hydratase (AH). The mono- and/or bis-alkyne precursors were reacted with NaTmMe and the resulting complexes [W(CO)(C2R2)(TmMe)Br] (R=H 1 , Me 2 ) oxidized to the target [WE(C2R2)(TmMe)Br] (E=O, R=H 4 , Me 5 ; E=S, R=H 6 , Me 7 ) using pyridine-N-oxide and methylthiirane. Halide abstraction with TlOTf in MeCN gave the cationic complexes [WE(C2R2)(MeCN)(TmMe)](OTf) (E=CO, R=H 10 , Me 11 ; E=O, R=H 12 , Me 13 ; E=S, R=H 14 , Me 15 ). Without MeCN, dinuclear complexes [W2O(μ-O)(C2Me2)2(TmMe)2](OTf)2 ( 8 ) and [W2(μ-S)2(C2Me2)(TmMe)2](OTf)2 ( 9 ) could be isolated showing distinct differences between the oxido and sulfido system with the latter exhibiting only one molecule of C2Me2. This provides evidence that a fine balance of the softness at W is important for acetylene coordination. Upon dissolving complex 8 in acetonitrile complex 13 is reconstituted in contrast to 9 . All complexes exhibit the desired stability toward water and the observed effective coordination of the scorpionate ligand avoids decomposition to disulfide, an often-occurring reaction in sulfur ligand chemistry. Hence, the data presented here point toward a mechanism with a direct coordination of acetylene in the active site and provide the basis for further model chemistry for acetylene hydratase. 相似文献
12.
Gaseous mixtures of germane or methylgermane with ammonia and methylgermane with phosphine have been studied by ion trap mass spectrometry. Rate constants of reactions of the primary ions and of the most important secondary ion species are reported, together with the calculated collisional rate constants and efficiencies of reaction. The GeHn+ (n = 0–3) ions, formed by electron ionization of both GeH4 and CH3GeH3, react with ammonia yielding, among others, the GeHn+ (n = 2–4) ion family, which, in a successive and slow reaction with NH3, only give the unreactive ammonium ion. Also, the CH3GeHn+ (n = 1, 2) species do not form Ge–N bonds, whereas secondary ions of germane, such as Ge2H2+, produce species containing germanium and nitrogen together. In the CH3GeH3/PH3 mixture a great number of ions are formed with rather high rate constants from primary ions of both reagent molecules and from phosphorus containing secondary ions. GePHn+ (n = 2–4) ions further react with methylgermane leading to cluster ions with increasing size such as Ge2PHn+ and Ge2CPHn+. The experimental conditions favoring the chain propagation of ions containing Ge and N, or Ge and P, with or without C, important in the chemical vapor deposition of materials of interest in photovoltaic technology, are discussed. 相似文献
13.
Unexpected Reduction of [Cp*TaCl4(PH2R)] (R = But, Cy, Ad, Ph, 2,4,6‐Me3C6H2; Cp* = C5Me5) by Reaction with DBU – Molecular Structure of [(DBU)H][Cp*TaCl4] (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) [Cp*TaCl4(PH2R)] (R = But, Cy, Ad, Ph, 2,4,6‐Me3C6H2 (Mes); Cp* = C5Me5) react with DBU in an internal redox reaction with formation of [(DBU)H][Cp*TaCl4] ( 1 ) (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) and the corresponding diphosphane (P2H2R2) or decomposition products thereof. 1 was characterised spectroscopically and by crystal structure determination. In the solid state, hydrogen bonding between the (DBU)H cation and one chloro ligand of the anion is observed. 相似文献
14.
Contributions to the Chemistry of Phosphorus. 240. On the Reactive Behaviour of Diphosphane-borane, P2H4 · BH3 Under mild temperature conditions, the thermal decomposition of diphosphane-borane ( 1 ) gives rise to the formation of phosphane-borane, PH3 · BH3, and triphosphane-2-borane, PH2? PH(BH3)? PH2 ( 2 ). In the presence of diphosphane-1,2-bis(borane), triphosphane-1,3-bis(borane), BH3? PH2? PH? PH2? BH3 ( 3 ), is formed additionally. The thermolysis product at room temperature is a polymeric solid of varying composition which contains phosphorus, boron, and hydrogen. Compound 1 reacts with metalating agents such as n-BuLi, LiBH4, and NaBH4 to furnish the borane-trihydrogendiphosphide ion, [PH2? PH? BH3]?, which immediately disproportionates to give the corresponding mono-and triphosphane derivatives. In the presence of an excess of THF-borane and in the case of a 1 : 1 molar ratio of 1 : NaBH4, the disproportionation does not occur and the new diphosphide derivative sodium-1,1,2-tris(borane)-1,2,2-trihydrogendiphosphide, Na[(BH3)2PH? PH2BH3] ( 4 ) can be obtained. The action of additional NaBH4 yields the diphosphide dianion with four coordinated BH3 groups. 相似文献
15.
《International journal of mass spectrometry and ion processes》1996,152(1):61-68
Gaseous mixtures of phosphine and germane have been investigated by ion trap mass spectrometry. Reaction pathways together with rate constants of the main reactions are reported. The mechanisms of ion/molecule reactions have been elucidated by single and multiple isolation steps. The GeHn+ (n = 1–3) ions react with phosphine to give GePHn+ (n = 2–4) ions. The GePH4+ ion further reacts with GeH4 to yield Ge2PH6+. The GePHn+ (n = 2–4) mixed ionic family also originates from the P+ phosphine primary ion, as well as from the P2Hn+ (n = 0–3) secondary ions of phosphine reacting with neutral germane and from Ge2H2+ reacting with phosphine. The main reaction pathways of the PHn+ (n = 0–2) ions with GeH4 lead to the formation of the GeH2+ and GeH3+ ionic species. Protonation of phosphine from different ionic precursors is a very common process and yields the stable phosphonium ion, PH4+. Trends in total abundances of secondary GePHn+ (n = 2–4) ions as function of reaction time for different PH3/GeH4 pressure ratios show that excess of germane slightly affects the nucleation of mixed Ge-P ions. 相似文献
16.
Zhanneta R. Gulyaeva Igor I. Patsanovsky Elenora A. Ishmaeva K. Micheal Pietrusiewicz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract A series of derivatives R1R2P(X)R3, where R1=R2=Ph. R3= -CH=CH-Me, X=O(I); R1=Me, R2=Ph, R3= -CH=CH2, X=O(II); R1=R2=Ph, R3= -CH=CH2, X=Se(III) and R1R2P(O)-CH2C(O)OX, where R1=Ph, R2= -CH=CH2, X=Ment?(IV); R1=Ph-2-OMe, R2=Ph, X=Ment?(V); R1=R2=CH2Ph, X=Et(I), were investigated by means of dipole moments method. The problem of conjugation in phosphorylethylenes and conformation behaviour of phosphorylacetates was considered. DM (exp.) of (I-IV), determined in CC14 solution are 4.48(I), 4.27(II), 4.97(III), 4.21(IV), 5.21(V) and 4.02 D (VI). The intramolecular electronic interactions of phosphoryl group with unsaturated fragment did not displays in polarity properties of compounds (I-III). The experimental dipole moments of derivatives (I-III) are equal to the calculated values of DM. DM (IV-VI) is very sensitive to orientation of the P=O and C=O polar bonds. Because DM (exp.) of these compounds very sensitive to its orientation. DM (calc.) for cis- and trans- orientation of P=O and C=O dipoles are really different, that allows to drow the conclution that, in the contrast to the crystal state, the corresponded dipoles prefer an anti array in solution. 相似文献
17.
Felix Krämer Dr. Michael Radius Dr. Alexander Hinz Melina E. A. Dilanas Prof. Dr. Frank Breher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(1):e202103974
The synthesis and full characterization of α-silylated (α-SiCPs; 1 – 7 ) and α-germylated (α-GeCPs; 11 – 13 ) phosphorus ylides bearing one chloride substituent R3PC(R1)E(Cl)R22 (R=Ph; R1=Me, Et, Ph; R2=Me, Et, iPr, Mes; E=Si, Ge) is presented. The molecular structures were determined by X-ray diffraction studies. The title compounds were applied in halide abstraction studies in order to access cationic species. The reaction of Ph3PC(Me)Si(Cl)Me2 ( 1 ) with Na[B(C6F5)4] furnished the dimeric phosphonium-like dication [Ph3PC(Me)SiMe2]2[B(C6F5)4]2 ( 8 ). The highly reactive, mesityl- or iPr-substituted cationic species [Ph3PC(Me)SiMes2][B(C6F5)4] ( 9 ) and [Ph3PC(Et)SiiPr2][B(C6F5)4] ( 10 ) could be characterized by NMR spectroscopy. Carrying out the halide abstraction reaction in the sterically demanding ether iPr2O afforded the protonated α-SiCP [Ph3PCH(Et)Si(Cl)iPr2][B(C6F5)4] ( 6 dec ) by sodium-mediated basic ether decomposition, whereas successfully synthesized [Ph3PC(Et)SiiPr2][B(C6F5)4] ( 10 ) readily cleaves the F−C bond in fluorobenzene. Thus, the ambiphilic character of α-SiCPs is clearly demonstrated. The less reactive germanium analogue [Ph3PC(Me)GeMes2][B{3,5-(CF3)2C6H3}4] ( 14 ) was obtained by treating 11 with Na[B{3,5-(CF3)2C6H3}4] and fully characterized including by X-ray diffraction analysis. Structural parameters indicate a strong CYlide−Ge interaction with high double bond character, and consequently the C−E (E=Si, Ge) bonds in 9 , 10 and 14 were analyzed with NBO and AIM methods. 相似文献
18.
Dominik Vítek Prof. Aleš Růžička Lise Vermeersch Dr. Libor Dostál Dr. Jan Turek Prof. Roman Jambor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202639
Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 ( 1 ; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 ( 2 ) and [LGe⋅BH3]2 ( 3 ) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 ( 4 ) and L(Cl)Ge⋅GaCl3 ( 5 ) without a GeII→B interaction. In 5 , an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed. 相似文献
19.
R2C=GeH2和R2Ge=CH2结构与成键特征的理论研究 总被引:2,自引:0,他引:2
用密度泛函理论(DFT), 在B3LYP/6-31+G(d, p)水平上研究了取代基对二取代锗烯R2Ge=CH2和R2C=GeH2 [R=H, OH, NH2, SH, PH2, F, Cl, Br, (NHCH)2, CH3, (CH)2]的影响. 研究发现π供电子取代基在碳上时更能引起分子结构在锗端的锥型化. 碳原子上的π电子给予取代基的给电子效应越强, R2C的单-三态能量差越大, π电子的反极化效应就越强, 使得化合物的结构在锗端发生的弯曲越明显, 从而使得弯曲结构更稳定. 和前人的计算相比, 碳上的给电子取代基对GeH2结构影响大于它对SiH2的影响. 相似文献
20.
Robert G. Carden Prof. Ross A. Widenhoefer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11026-11030
The gold sulfonium benzylide complexes [( P1 )AuCHPh(SR1R2)]+ {B[3,5-CF3C6H3]4}− [ P1 =P(tBu)2o-biphenyl; R1, R2=-(CH2)4- ( 1 a ); R1=Et, R2=Ph ( 1 b ); R1=R2=Ph ( 1 c )] were synthesized by reaction of the gold α-chloro benzyl complex ( P1 )AuCHClPh with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and excess sulfide. Complexes 1 undergo efficient benzylidene transfer to alkenes and DMSO under mild conditions without external activation. Kinetic analysis of the reaction of 1 c with styrene was consistent with the intermediacy of the cationic gold benzylidene complex [( P1 )AuCHPh]+ ( I ). 相似文献