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1.
Synthesis, Structure, and Photochemical Behavior of Olefine Iridium(I) Complexes with Acetylacetonato Ligands The bis(ethene) complex [Ir(κ2‐acac)(C2H4)2] ( 1 ) reacts with tertiary phosphanes to give the monosubstitution products [Ir(κ2‐acac)(C2H4)(PR3)] ( 2 – 5 ). While 2 (R = iPr) is inert toward PiPr3, the reaction of 2 with diphenylacetylene affords the π‐alkyne complex [Ir(κ2‐acac)(C2Ph2)(PiPr3)] ( 6 ). Treatment of [IrCl(C2H4)4] with C‐functionalized acetylacetonates yields the compounds [Ir(κ2‐acacR1,2)(C2H4)2] ( 8 , 9 ), which react with PiPr3 to give [Ir(κ2‐acacR1,2)(C2H4)(PiPr3)] ( 10 , 11 ) by displacement of one ethene ligand. UV irradiation of 5 (PR3 = iPr2PCH2CO2Me) and 11 (R2 = (CH2)3CO2Me) leads, after addition of PiPr3, to the formation of the hydrido(vinyl)iridium(III) complexes 7 and 12 . The reaction of 2 with the ethene derivatives CH2=CHR (R = CN, OC(O)Me, C(O)Me) affords the compounds [Ir(κ2‐acac)(CH2=CHR)(PiPr3)] ( 13 – 15 ), which on photolysis in the presence of PiPr3 also undergo an intramolecular C–H activation. In contrast, the analogous complexes [Ir(κ2‐acac)(olefin)(PiPr3)] (olefin = (E)‐C2H2(CO2Me)2 16 , (Z)‐C2H2(CO2Me)2 17 ) are photochemically inert. 相似文献
2.
The Tsuji—Trost allylation of CH acids, in particular, those of the YCH2CO2Et type (Y = CO2Et, C(O)Me, CN), with allylic acetates in the K2CO3—DMF system in the presence of palladium catalysts with ligands RN(PPh2)2 (R = Ph, Pri, c-C6H11) is accomplished. 相似文献
3.
Stefan Sander Dr. Robert Müller Dr. Mike Ahrens Prof. Dr. Martin Kaupp Prof. Dr. Thomas Braun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(57):14287-14298
The reaction of [PtCl2(COD)] (COD=1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr2P(C9H8N)) led to the formation of the platinum(ii ) chlorido complexes, cis-[PtCl2{iPr2P(C9H8N)}2] ( 1 ) and trans-[PtCl2{iPr2P(C9H8N)}2] ( 2 ). The cis-complex 1 reacted with NEt3 yielding the complex cis-[PtCl{κ2-(P,N)-iPr2P(C9H7N)}{iPr2P(C9H8N)}] ( 3 ) bearing a cyclometalated κ2-(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt3. Treatment of 1 or 3 with (CH3)4NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{κ2-(P,N)-iPr2P(C9H7N)}2] ( 4 ). The molecular structures of the complexes 1–4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF{κ2-(P,N)-iPr2P(C9H7N)}{iPr2P(C9H8N)}] ⋅ (HF)4 ( 5 ⋅ (HF)4) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii ) fluorido complex 5 ⋅ (HF)4 exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3 , complex 5 ⋅ (HF)4 reacted with CO or the ynamide 1-(2-phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){κ2-(P,C)-iPr2P(C9H7NCO)}{iPr2P(C9H8N)}][F(HF)4] ( 7 ) and a complex, which we suggest to be cis-[Pt{C=C(Ph)OCN(C3H6)}{κ2-(P,N)-iPr2P(C9H7N)}{iPr2P(C9H8N)}][F(HF)4] ( 9 ), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9 . 相似文献
4.
M. Sc. Abolghasem Bakhoda Quan Jiang Dr. Jeffery A. Bertke Prof. Thomas R. Cundari Prof. Dr. Timothy H. Warren 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(23):6526-6530
We report herein three new modes of reactivity between arylazides N3Ar with a bulky copper(I) β-diketiminate. Addition of N3ArX3 (ArX3=2,4,6-X3C6H2; X=Cl or Me) to [iPr2NN]Cu(NCMe) results in triazenido complexes from azide attack on the β-diketiminato backbone. Reaction of [iPr2NN]Cu(NCMe) with bulkier azides N3Ar leads to terminal nitrenes [iPr2NN]Cu]=NAr that dimerize via formation of a C−C bond at the arylnitrene p-position to give the dicopper(II) diketimide 4 (Ar=2,6-iPr2C6H3) or undergo nitrile insertion to give diazametallocyclobutene 8 (Ar=4-Ph-2,6-iPr2C6H2). Importantly, reactivity studies reveal both 4 and 8 to be “masked” forms of the terminal nitrenes [iPr2NN]Cu=NAr that undergo nitrene group transfer to PMe3, tBuNC, and even into a benzylic sp3 C−H bond of ethylbenzene. 相似文献
5.
Addition Reactions of Me3SiCN with Aldehydes Catalyzed by Aluminum Complexes Containing in their Coordination Sphere O,S, and N Ligands
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Prof. Zhi Yang Yafei Yi Dr. Mingdong Zhong Sriman De Totan Mondal Dr. Debasis Koley Dr. Xiaoli Ma Dr. Dongxiang Zhang Prof. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(20):6932-6938
The reaction of one equivalent of LAlH2 ( 1 ; L=HC(CMeNAr)2, Ar=2,6‐iPr2C6H3, β‐diketiminate ligand) with two equivalents of 2‐mercapto‐4,6‐dimethylpyrimidine hydrate resulted in LAl[(μ‐S)(m‐C4N2H)(CH2)2]2 ( 2 ) in good yield. Similarly, when N‐2‐pyridylsalicylideneamine, N‐(2,6‐diisopropylphenyl)salicylaldimine, and ethyl 3‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐2‐carboxylate were used as starting materials, the corresponding products LAl[(μ‐O)(o‐C6H4)CN(C5NH4)]2 ( 3 ), LAlH[(μ‐O)(o‐C4H4)CN(2,6‐iPr2C6H3)] ( 4 ), and LAl[(μ‐NH)(o‐C8SH8)(COOC2H5)]2 ( 5 ) were isolated. Compounds 2 – 5 were characterized by 1H and 13C NMR spectroscopy as well as by single‐crystal X‐ray structural analysis. Surprisingly, compounds 2 – 5 exhibit good catalytic activity in addition reactions of aldehydes with trimethylsilyl cyanide (TMSCN). 相似文献
6.
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
7.
Iridium(I) and Iridium(III) Complexes with Triisopropylarsane as Ligand The ethene complex trans‐[IrCl(C2H4)(AsiPr3)2] ( 2 ), which was prepared from [IrCl(C2H4)2]2 and AsiPr3, reacted with CO and Ph2CN2 by displacement of ethene to yield the substitution products trans‐[IrCl(L)(AsiPr3)2] ( 3 : L = CO; 4 : L = N2). UV irradiation of 2 in the presence of acetonitrile gave via intramolecular oxidative addition the hydrido(vinyl)iridium(III) compound [IrHCl(CH=CH2)(CH3CN)(AsiPr3)2] ( 5 ). The reaction of 2 with dihydrogen led under argon to the formation of the octahedral complex [IrH2Cl(C2H4)(AsiPr3)2] ( 7 ), whereas from 2 under 1 bar H2 the ethene‐free compound [IrH2Cl(AsiPr3)2] ( 6 ) was generated. Complex 6 reacted with ethene to afford 7 and with pyridine to give [IrH2Cl(py)(AsiPr3)2] ( 8 ). The mixed arsane(phosphane)iridium(I) compound [IrCl(C2H4)(PiPr3)(AsiPr3)] ( 11 ) was prepared either from the dinuclear complex [IrCl(C2H4)(PiPr3)]2 ( 9 ) and AsiPr3 or by ligand exchange from [IrCl(C2H4)(PiPr3)(SbiPr3)] ( 10 ) und triisopropylarsane. The molecular structure of 5 was determined by X‐ray crystallography. 相似文献
8.
Connor S. MacNeil Prof. Dr. Paul G. Hayes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8203-8207
Divergent reactivity of organometallic rhodium(I) complexes, which led to the isolation of neutral rhodium silylenes, is described. Addition of PhRSiH2 (R=H, Ph) to the rhodium cyclooctene complex (iPrNNN)Rh(COE) (1-COE; iPrNNN=2,5-[iPr2P=N(4-iPrC6H4)]2N(C6H2)−, COE=cyclooctene) resulted in the oxidative addition of an Si−H bond, providing rhodium(III) silyl hydride complexes (iPrNNN)Rh(H)SiHRPh (R=H, 2 -SiH2Ph; Ph, 2 -SiHPh2). When the carbonyl complex (iPrNNN)Rh(CO) ( 1 -CO) was treated with hydrosilanes, base-stabilized rhodium(I) silylenes κ2-N,N-(iPrNNN)(CO)Rh=SiRPh (R=H, 3 -SiHPh; Ph, 3 -SiPh2) were isolated and characterized using multinuclear NMR spectroscopy and X-ray crystallography. Both silylene species feature short Rh−Si bonds [2.262(1) Å, 3 -SiHPh; 2.2702(7) Å, 3 -SiPh2] that agree well with the DFT-computed structures. The overall reaction led to a change in the iPrNNN ligand bonding mode (κ3→κ2) and loss of H2 from PhSiRH2, as corroborated by deuterium labelling experiments. 相似文献
9.
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
10.
Dr. Beatriz Eguillor Prof. Dr. Miguel A. Esteruelas Virginia Lezáun Dr. Montserrat Oliván Dr. Enrique Oñate Dr. Jui‐Yi Tsai Dr. Chuanjun Xia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9106-9110
A MHC6 complex of a platinum group metal with a capped octahedral arrangement of donor atoms around the metal center has been characterized. This osmium compound OsH{κ2‐C,C‐(PhBIm‐C6H4)}3, which reacts with HBF4 to afford the 14 e? species [Os{κ2‐C,C‐(PhBIm‐C6H4)}(Ph2BIm)2]BF4 stabilized by two agostic interactions, has been obtained by reaction of OsH6(PiPr3)2 with N,N′‐diphenylbenzimidazolium chloride ([Ph2BImH]Cl) in the presence of NEt3. Its formation takes place through the C,C,C‐pincer compound OsH2{κ3‐C,C,C‐(C6H4‐BIm‐C6H4)}(PiPr3)2, the dihydrogen derivative OsCl{κ2‐C,C‐(PhBIm‐C6H4)}(η2‐H2)(PiPr3)2, and the five‐coordinate osmium(II) species OsCl{κ2‐C,C‐(PhBIm‐C6H4)}(PiPr3)2. 相似文献
11.
Melike Bayram Sebastian Gondzik Dieter Bläser Christoph Wölper Stephan Schulz 《无机化学与普通化学杂志》2016,642(15):847-852
Reactions of bis(phosphinimino)methanes H2C(PPh2NR)2 [R = SiMe3 (L1H), Ph (L2H), 2,6‐iPr2‐C6H3 (DIPP) (L3H)] with ZnR2 (R = Me, Et) yielded the corresponding bis(phosphinimino)methanide zinc complexes LZnMe [L2 ( 1 ), L3 ( 2 )] and LZnEt [L1 ( 3 ), L2 ( 4 ), and L3 ( 5 )]. Complexes 1 – 5 were characterized by heteronuclear NMR (1H, 13C, 31P) and IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. 相似文献
12.
Dr. Christoph Helling Lars J. C. van der Zee Jelle Hofman Felix J. de Zwart Dr. Simon Mathew Dr. Martin Nieger Assoc. Prof. Dr. J. Chris Slootweg 《Angewandte Chemie (International ed. in English)》2023,62(48):e202313397
Herein, we present the formation of transient radical ion pairs (RIPs) by single-electron transfer (SET) in phosphine−quinone systems and explore their potential for the activation of C−H bonds. PMes3 (Mes=2,4,6-Me3C6H2) reacts with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) with formation of the P−O bonded zwitterionic adduct Mes3P−DDQ ( 1 ), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6-iPr3C6H2) afforded C−H bond activation product Tip2P(H)(2-[CMe2(DDQ)]-4,6-iPr2-C6H2) ( 2 ). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3]⋅+[DDQ]⋅−, and subsequent homolytic C−H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2P(H)(2-[CMe2{TCQ−B(C6F5)3}]-4,6-iPr2-C6H2) ( 4 , TCQ=tetrachloro-1,4-benzoquinone) and Tip2P(H)(2-[CMe2{oQtBu−B(C6F5)3}]-4,6-iPr2-C6H2) ( 8 , oQtBu=3,5-di-tert-butyl-1,2-benzoquinone), from reactions of PTip3 with Lewis-acid activated quinones, TCQ−B(C6F5)3 and oQtBu−B(C6F5)3, respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C−H bond activation by the synergistic action of radical ion pairs. 相似文献
13.
H. Werner H. Otto Tri Ngo-Khac Ch. Burschka 《Journal of organometallic chemistry》1984,262(1):123-136
The complexes C5H5CuPR3 (R = Me, Pri), C5H5AuPR3 (R = Me, Pri), C5Me5CuPR3 (R = Me, Pri, Ph) and C5Me5AuPR3 (R = Pri, Ph) are prepared from [ClCuPR3]n or ClAuPR3 and LiC5H5 (TlC5H5) or LiC5Me5, respectively. According to the 1H and 13C NMR spectra, the cyclopentadienyl and pentamethylcyclopentadienylgold compounds are fluxional in solution. The X-ray crystal structure of C5H5AuPPr3i has been determined at ?120°C. The gold atom is in a linear arrangement (PAuC(1) = 177.0(2)°) and primarily σ-bonded to the cyclopentadienyl ring which shows a weak “slip distortion” toward a η3-mode of coordination. The complexes C5R′5AuPR3 (R′ = H, Me) and C5Me5CuPPr3i react with 1-alkynes such as C2H2, HC2Ph and HC2CO2Me to form alkinylgold and copper compounds R″C2MPR3. They have been characterized by IR, UV and NMR (1H, 13C, 31P) spectroscopy. 相似文献
14.
Matthias Mawick Carolin Jaworski Jens Bittermann Dr. Ljuba Iovkova Yinglan Pu Prof. Dr. Carmen Wängler Prof. Dr. Björn Wängler Prof. Dr. Klaus Jurkschat Prof. Dr. Norbert Krause Prof. Dr. Ralf Schirrmacher 《Angewandte Chemie (International ed. in English)》2023,62(50):e202309002
The ring-opening Si-fluorination of a variety of azasilole derivatives cyclo-1-(iPr2Si)−4-X−C6H3−2-CH2NR ( 4 : R=2,6-iPr2C6H3, X=H; 4 a : R=2,4,6-Me3C6H2, X=H; 9 : R=2,6-iPr2C6H3, X=tBuMe2SiO; 10 : R=2,6-iPr2C6H3, X=OH; 13 : R=2,6-iPr2C6H3, X=HCCCH2O; 22 : R=2,6-iPr2C6H3, X=tBuMe2SiCH2O) with different 19F-fluoride sources was studied, optimized and the experience gained was used in a translational approach to create a straightforward 18F-labelling protocol for the azasilole derivatives [18F] 6 and [18F] 14 . The latter constitutes a potential clickable CycloSiFA prosthetic group which might be used in PET tracer development using Cu-catalysed triazole formation. Based on our findings, CycloSiFA has the potential to become a new entry into non-canonical labelling methodologies for radioactive PET tracer development. 相似文献
15.
Dr. Tetsuya Fukuda Dr. Hisako Hashimoto Prof. Dr. Shigeyoshi Sakaki Prof. Dr. Hiromi Tobita 《Angewandte Chemie (International ed. in English)》2016,55(1):188-192
Treatment of pyridine‐stabilized silylene complexes [(η5‐C5Me4R)(CO)2(H)W?SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N‐heterocyclic carbene MeIiPr (1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η5‐C5Me4R)(CO)2W?SiH(Tsi)][HMeIiPr] (R=Me ( 1‐Me ); R=Et ( 1‐Et )). Subsequent oxidation of 1‐Me and 1‐Et with pyridine‐N‐oxide (1 equiv) gave anionic η2‐silaaldehydetungsten complexes [(η5‐C5Me4R)(CO)2W{η2‐O?SiH(Tsi)}][HMeIiPr] (R=Me ( 2‐Me ); R=Et ( 2‐Et )). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis. 相似文献
16.
Rocco Alessio Daniela Belli Dell'Amico Fausto Calderazzo Ulli Englert Alessandro Guarini Luca Labella Peter Strasser 《Helvetica chimica acta》1998,81(2):219-230
The reaction of CuO'Bu with CO2, and iPr2NH in the presence of PPh3, gives the dialkylcarbamato complex [Cu(O2CNiPr2)(PPh3)2] ( 1 ). The CO2/R2NH system (R = Me, Et) in an appropriate organic medium reacts with Ag2O giving the corresponding N,N-dialkylcarbamato complexes of analytical formula [Ag(C2CNR2)] (R = Me, 2 ; R = Et, 3 ). The methyl derivative 2 was characterized by X-ray diffraction methods. Crystal data of 2 : for [Ag2(O2CNMe2)2], C6H12Ag2N2O4, mol. wt. 391.9; monoclinic, space group P21/c, a = 12.08(1), b = 3.797(2), c = 11.316(7) Å, β = 113.37(6)°, V = 476.3 Å3, Z = 2, Dc = 2.732 g cm?3; μ(MoKα) = 40.64 cm?1, F(000) = 376.0; R = 0.059, Rw = 0.067; g.o.f. 1.27. The structure consists of dinuclear [(Ag2OCNMe2)2] units with slightly distorted linearly two-coordinated Ag-atoms containing bridging carbamato groups to form a substantially planar eight-membered ring with an intra-annular Ag? Ag distance of 2.837(2) Å; the dinuclear units are further joined by Ag? O bonds to form an infinite array. Compound 3 , which is presumably dinuclear, as suggested by cryoscopic measurements in benzene, undergoes a structural fission with PPh3, giving the mononuclear triphenylphosphine derivative [Ag(O2CNEt2)(PPh3)2] ( 4 ). The amine-catalyzed conversion of Ag2O into Ag2CO3, in the presence of the iPr2NH/CO2 system, is also reported. Cl-Exchange from [AuCl(PPh3)] with [Ag(O2CNEt2)] ( 3 ) gives the first N,N-dialkylcarbamato complex of gold, namely [Au(O2CNEt2)(PPh3)] ( 5 ), which crystallizes in the monoclinic system: C23H25AuNO2P · 0.5 C7H16, mol. wt. 625.5, space group P21/c; a = 13.212(5), b = 12.25(1), c = 16.795(6) Å, β = 109.09(2)°, V = 2568(2) Å3, Z = 4, Dc, = 1.618 g cm?3; μ(AgKα) = 31.40 cm?1, F(000) = 1236.0; R = 0.058; Rw = 0.064; g.o.f. 2.121. The compound contains two-coordinated Au-atom, namely to the P-atom and to the O-atom of the monodentate carbamato group, the P? Au? O bond angle being 174.7(3)°. The reaction with MeI showed these compounds to react predominantly at the carbamato O-atom giving the corresponding urethanes R2NCO2Me. Evidence was gathered for the transient coordination of CO to Ag in 3 . 相似文献
17.
Bruno Chaudret 《Journal of organometallic chemistry》1984,268(2):c33-c37
Complexes of the type RuH4P3 (P=P(Pri)3, P(C6H11)3 or P(N(C2H5)2)3) in solution in deuterated aromatic solvents undergo H-D exchange between the solvent and the coordinated phosphines. The reaction works better with RuH4P(Pri3)3, in which about 70% of the phosphine protons can be so exchanged. A mechanism involving dissociation of a phosphine followed by activation of the solvent CD bond and the phosphine CH bond is proposed. 相似文献
18.
In this work we report the synthesis and characterisation of the 1.5‐diphosphanyldiethylether O{C2H4PH(SiiPr3)}2 ( 2 ) in which two silyl‐substituted phosphine groups are linked by an ether bridge as well as the compound O(SiiPr2PHEt)2 ( 3 ) where two ethyl substitute phosphine groups are connected by a siloxane bridge. In addition, we describe the metalation of 2 and 3 with triisopropylindium. These reactions lead to the compounds [O{C2H4P(SiiPr3)IniPr2}2] ( 4 ) and [O{SiiPr2P(Et)IniPr2}2] ( 5 ) with In2P2 ring structures. 相似文献
19.
X-Ray Structure of [Li(tmeda)2][Zn(2,4,6- i Pr3C6H2)3] A side reaction of zinc halide containing VCl2(tmeda)2 and Li(2,4,6-iPr3C6H2) formed [Li(tmeda)2][Zn(2,4,6-iPr3C6H2)3] · 0,5[(tmeda)Li(μ-Cl)]2. The crystal structure (orthorhombic, Pbca, a = 26,226(2), b = 19,739(2), c = 27,223(5) Å, Z = 8, R = 0,062, wR2 = 0,154) contains trigonal planar zinc anions with Zn–C distances of 2,039(7) Å (average) and a propeller like arrangement of the aryl rings. 相似文献
20.
Maxime Boudjelel Richard Declercq Sonia Mallet-Ladeira Ghenwa Bouhadir Didier Bourissou 《无机化学与普通化学杂志》2020,646(13):561-564
The vinyl carbenoid H2C=CBr(Li) has been used as key precursor to prepare a geminal C(sp2)-bridged phosphine-borane. Starting from bromoethene, two sequences of lithiation/electrophilic trapping, with ClPiPr2 and FBMes2 respectively, affords iPr2P–C(=CH2)–BMes2 3 [Mes = 2,4,6-(H3C)3C6H2]. This new phosphine-borane 3 was characterized by multi-nuclear NMR and mass spectroscopy. It adopts a monomeric open structure without P→B interaction. A few crystals of a secondary product 4 were analyzed by X-ray diffraction, revealing an unusual dimeric structure. 相似文献