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1.
Bettina Bechlars Robert Feuerhake Dieter Fenske Prof. Dr. Dr.h.c. 《无机化学与普通化学杂志》2007,633(15):2603-2613
Syntheses and Crystal Structures of Novel Chalcogenido‐bridged Niobium Copper Clusters In the presence of tertiary phosphines, the reaction of NbCl5 and Copper(I) salts with Se(SiMe3)2 (E = S, Se) affords the new chalcogenido‐bridged niobium‐copper cluster compounds ( 1 ) and [NbCu4Se4Cl (PPh3)4] ( 2 ). Using E(R)SiMe3 (E = S, Se, R = Ph, nPr) instead of the bisilylated selenium species leads to the compounds [NbCu2(SPh)6(PMe3)2] ( 3 ), [NbCu2(SPh)6(PnPr3)2] ( 4 ), [NbCu2(SePh)6(PMe3)2] ( 5 ), [NbCu2(SePh)6(PnPr3)2] ( 6 ), [NbCu2(SePh)6(PiPr3)2] ( 7 ), [NbCu2(SePh)6(PtBu3)2] ( 8 ), [NbCu2(SePh)6(PiPr2Me)2] ( 9 ), [NbCu2(SePh)6(PPhEt2)2] ( 10 ), [Nb2Cu2(SnPr)8(PnPr3)2Cl2] ( 11 ) and [Nb2Cu6(SnPr)12(PiPr3)2Cl4]·2 CH3CN ( 12 ·2 CH3CN). By reacting CuI salts and NbCl5 with the monosilylated selenides Se(tBu)SiMe3 and Se(iPr)SiMe3 which have a weak Se–C bond the products [Nb2Cu6Se6(PiPr3)6Cl4] ( 13 ), [Nb2Cu4Se2(SeiPr)6(PnPr3)4Cl2] ( 14 ) and [Nb2Cu6Se2(SeiPr)10(PEt2Me)2Cl2]·DME ( 15 ) are formed which contain selenide as well as alkylselenolate ligands. The molecular structures of all of these new compounds were determined by single crystal X‐ray diffraction measurements. 相似文献
2.
Synthesis and Characterization of New Cyclic and Cage‐like Indium — Phosphorus and Indium — Arsenic Compounds The reaction of InEt3 with H2ESiiPr3 initially yields the cyclic compound [Et2InP(H)SiiPr3]2 ( 2 ). 2 appears as a mixture of cis and trans isomers and has been characterized by 31P‐NMR spectroscopy, IR spectroscopy, and mass spectrometry. 2 decomposes in solution under elimination of ethane during a few days to form [EtInPSiiPr3]4 ( 3 ) with a cage‐like structure. The analogous arsenic compound [EtInAsSiiPr3]4 ( 4 ) can be prepared by reaction of InEt3 with H2AsSiiPr3. Central structural motif of 3 and 4 is an In4E4 heterocubane like structure (E = P, As), whereas the reaction of InEt3 with H2PSiMe2Thex (Thex = CMe2iPr) yields [EtInPSiMe2Thex]6 ( 5 ) with a hexagonal prismatic structure. 相似文献
3.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):233-243
Reaction of the secocubane [Sn3(μ2‐NHtBu)2(μ2‐NtBu)(μ3‐NtBu)] ( 1 ) with dibutylmagnesium produces the heterobimetallic cubane [Sn3Mg(μ3‐NtBu)4] ( 4 ) which forms the monochalcogenide complexes of general formula [ESn3Mg(μ3‐NtBu)4] ( 5 a , E=Se; 5 b , E=Te) upon reaction with elemental chalcogens in THF. By contrast, the reaction of the anionic lithiated cubane [Sn3Li(μ3‐NtBu)4]? with the appropriate quantity of selenium or tellurium leads to the sequential chalcogenation of each of the three SnII centres. Pure samples of the mono‐ or dichalcogenides are, however, best obtained by stoichiometric redistribution reactions of [Sn3Li(μ3‐NtBu)4]? and the trichalcogenides [E3Sn3Li(μ3‐NtBu)4]? (E=Se, Te). These reactions are conveniently monitored by using 119Sn NMR spectroscopy. The anion [Sn3Li(μ3‐NtBu)4]? also acts as an effective chalcogen‐transfer reagent in reactions of selenium with the neutral cubane [{Snμ3‐N(dipp)}4] ( 8 ) (dipp=2,6‐diisopropylphenyl) to give the dimer [(thf)Sn{μ‐N(dipp)}2Sn(μ‐Se)2Sn{μ‐N(dipp)}2Sn(thf)] ( 9 ), a transformation that results in cleavage of the Sn4N4 cubane into four‐membered Sn2N2 rings. The X‐ray structures of 4 , 5 a , 5 b , [Sn3Li(thf)(μ3‐NtBu)4(μ3‐Se)(μ2‐Li)(thf)]2 ( 6 a ), [TeSn3Li(μ3‐NtBu)4][Li(thf)4] ( 6 b ), [Te2Sn3Li(μ3‐NtBu)4][Li([12]crown‐4)2] ( 7 b′′ ) and 9 are presented. The fluxional behaviour of cubic imidotin chalcogenides and the correlation between NMR coupling constants and tin–chalcogen bond lengths are also discussed. 相似文献
4.
Matthias Westerhausen Mathias Krofta Stefan Schneiderbauer Holger Piotrowski 《无机化学与普通化学杂志》2005,631(8):1391-1396
Transmetallation of Tin(II) in [Sn(μ3‐PSitBu3)]4 by Barium – from Sn4P4 Heterocubane Structures to Heterobinuclear Cage Compounds with a Central BanSn4?nP4 Heterocubane Polyhedron (n = 1, 2 and 3) For the preparation of compounds of the type [BanSn4?n(PSitBu3)4] (n = 1 ( 2 ), 2 ( 3 ) and 3 ( 4 )) two synthetic routes are applicable: in the transmetallation reaction homometallic [Sn4(PSitBu3)4] ( 1 ) reacts with barium metal and in a deprotonation reaction (metallation) tri(tert‐butyl)silylphosphane reacts simultaneously with (thf)2Ba[N(SiMe3)2]2 and Sn[N(SiMe3)2]2. During the transmetallation reaction mixtures of the heterobimetallic cage compounds 2 to 4 are obtained, however, analytically pure compounds 2 and 3 are accessible by the metallation reaction. Compound 4 is formed as a minor product together with 3 . Due to the larger Ba‐P bond lengths compared to the Sn‐P values the substitution of tin by barium leads to strong distortions of the heterocubane moiety. With NMR‐spectroscopic experiments one could show that all the above mentioned compounds form BanSn4?nP4 heterocubane cage structures. 相似文献
5.
Bisaminophosphanes – Synthesis, Structure, and Reactivity Different pathways for the synthesis of bis(alkylamino)phosphanes RP(N(H)R′)2 are described. t‐BuP(N(H)‐ Dipp)2 (Dipp = 2,6‐i‐Pr2–C6H3) was structurally characterized by single crystal X‐ray diffraction. The reactivity of the compounds was examplarily investigated using t‐BuP(N(H)t‐Bu)2. Its reaction with Me3Al and R2AlH (R = Me, Et, i‐Bu) in 1 : 1 and 1 : 2 stoichiometrie yield monosubstituted compounds of the type t‐BuP(N(H)t‐Bu)(N(AlR2)t‐Bu). 相似文献
6.
Synthesis and Crystal Structures of Copper Zinc Phenylthiolate and the First Copper Zinc Selenolate and Tellurolate Complexes 
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下载免费PDF全文 Five copper zinc phenylchalcogenolate complexes [(iPr3PCu)3(ZnMe2)2(SPh)3] ( 1 ), [(iPr3PCu)2(ZnPh)4(SPh)6] ( 2 ), [(iPr3PCu)2(ZnEt)4(SPh)6] ( 3 ), [(iPr3PCu)3(ZnEt)(SePh)4] ( 4 ), and [(iPr3PCu)3Cu(iPr3PZn)(TePh)6] ( 5 ) were synthesized by the reaction of phosphine stabilized copper phenylchalcogenolate complexes with ZnR2 (R = Me, Et, Ph) with and without additional chalcogenol. The novel mixed metal compounds were characterized by single‐crystal X‐ray structure analysis and NMR spectroscopy. 4 and 5 are the first examples of compounds with a Zn–Se–Cu or a Zn–Te–Cu linkage, respectively. 相似文献
7.
Ligandstabilisierte cyclische und polycyclische Aluminium‐Phosphor‐ und Aluminium‐Arsen‐Verbindungen
Carsten von Hnisch 《无机化学与普通化学杂志》2003,629(9):1496-1500
Ligand Stabilized Cyclic and Polycyclic Aluminium Phosphorus and Aluminium Arsenic Compounds The reaction of AlCl3 with Li2AsSiRMe2 (R = CMe2iPr) in a mixture of ether and heptane yields the ether stabilized polycyclic compound [(AlCl)4(AsSiRMe2)4(Et2O)2] ( 4 ) with a ladder shaped Al4As4 core structure. The shape of 4 is mostly similar to the aluminium phosphorus compound [(AlCl)4(PSiiPr3)4(Et2O)2] ( 1 ) described recently [1]. These two compounds 1 and 4 can be cleaved into the cyclic compounds [{AlCl(C5H5N)}2(PSiiPr3)2] ( 3 ) and [{AlCl(NEt3)}2(AsSiRMe2)2] ( 5 ) by reaction with pyridine and NEt3, respectively. The compounds 3 , 4 , and 5 have been characterized by single crystal X‐ray diffraction. 相似文献
8.
New Copper Complexes Containing Phosphaalkene Ligands. Molecular Structure of [Cu{P(Mes*)C(NMe2)2}2]BF4 (Mes* = 2,4,6‐tBu3C6H2) Reaction of equimolar amounts of the inversely polarized phosphaalkene tBuP=C(NMe2)2 ( 1a ) and copper(I) bromide or copper(I) iodide, respectively, affords complexes [Cu3X3{μ‐P(tBu)C(NMe2)2}3] ( 2 ) (X =Br) and ( 3 ) (X = I) as the formal result of the cyclotrimerization of a 1:1‐adduct. Treatment of 1a with [Cu(L)Cl] (L = PiPr3; SbiPr3) leads to the formation of compounds [CuCl(L){P(tBu)C(NMe2)2}] ( 4a ) (L = PiPr3) and ( 4b ) (L = SbiPr3), respectively. Reaction of [(MeCN)4Cu]BF4 with two equivalents of PhP=C(NMe2)2 ( 1b ) yields complex [Cu{P(Ph)C(NMe2)2}2]BF4 ( 5b ). Similarly, compounds [Cu{P(Aryl)C(NMe2)2}2]BF4 ( 5c (Aryl = Mes and 5d (Aryl = Mes*)) are obtained from ArylP=C(NMe2)2 ( 1c : Aryl = Mes; 1d : Mes*) and [(MeCN)4Cu]BF4 in the presence of SbiPr3. Complexes 2 , 3 , 4a , 4b , and 5b‐5d are characterized by means of elemental analyses and spectroscopy (1H‐, 13C{1H}‐, 31P{1H}‐NMR). The molecular structure of 5d is determined by X‐ray diffraction analysis. 相似文献
9.
The reaction of the NHC iPr2Im [NHC=N‐heterocyclic carbene, iPr2Im = 1, 3‐bis(isopropyl)imidazolin‐2‐ylidene] with freshly prepared NiBr2 in thf or dme results in the formation of the air stable nickel(II) complex trans‐[Ni(iPr2Im)2Br2] ( 2 ). Complex 2 was structurally characterized. Thermal analysis (DTA/TG) reveals a very high decomposition temperature of 298 °C. Reduction of 2 with sodium or C8K in the presence of the olefins COD (cyclooctadiene) or COE (cyclooctene) affords the highly reactive compounds [Ni2(iPr2Im)4(COD)] ( 1 ) and [Ni(iPr2Im)2(COE)] ( 4 ). Alkylation of 2 with organolithiums leads to the formation of trans‐[Ni(iPr2Im)2(R)2] [R = Me ( 5 ), CH2SiMe3 ( 6 )], whereas the reaction of 2 with LiCp* [Cp* = (η5‐C5(CH3)5)] at 80 °C causes the loss of one NHC ligand and affords [(η5‐C5(CH3)5)Ni(iPr2Im)Br] ( 7 ). 相似文献
10.
The reaction of iPr2Si(PH2)2 ( 1 ) with [Ca{N(SiMe3)2}2(THF)2] at 25 °C in molar ratio 1:1 yields the compound [Ca3{iPr2Si(PH)2}3(THF)6] ( 2 ). Compound 2 consists of two Ca2P3 trigonal bipyramids with one conjoint calcium corner and SiiPr2 bridged phosphorus atoms. In contrast, the same reaction at 60 °C yield the complex [Ca({P(SiiPr2)2PH}2(THF)4] ( 3 ). The isotype strontium compound [Sr({P(SiiPr2)2PH}2(THF)4] ( 4 ) was obtained from the reaction of iPr2Si(PH2)2 with [Sr{N(SiMe3)2}2(DME)2]. The Compounds 2 – 4 were characterised by single crystal X‐ray diffraction, elemental analysis as well as IR and NMR spectroscopic techniques. 相似文献
11.
On the Reactivity of Silylated Ge9 Clusters: Synthesis and Characterization of [ZnCp*(Ge9{Si(SiMe3)3}3)], [CuPiPr3(Ge9{Si(SiMe3)3}3)], and [(CuPiPr3)4{Ge9(SiPh3)2}2] 下载免费PDF全文
下载免费PDF全文 Kerstin Mayer Lorenz J. Schiegerl Prof. Dr. Thomas F. Fässler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18794-18800
We report on the synthesis of new derivatives of silylated clusters of the type [Ge9(SiR3)3]? (R = SiMe3, Me = CH3; R = Ph, Ph = C6H5) as well as on their reactivity towards copper and zinc compounds. The silylated cluster compounds were synthesized by heterogeneous reactions starting from the Zintl phase K4Ge9. Reaction of K[Ge9{Si(SiMe3)3}3] with ZnCl2 leads to the already known dimeric compound [Zn(Ge9{Si(SiMe3)3}3)2] ( 1 ), whereas upon the reaction with [ZnCp*2] the coordination of [ZnCp*]+ to the cluster takes place (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) under the formation of [ZnCp*(Ge9{Si(SiMe3)3}3)] ( 2 ). A similar reaction leads to [CuPiPr3(Ge9{Si(SiMe3)3}3)] ( 3 ) from [CuPiPr3Cl] (iPr=isopropyl). Further we investigated the novel silylated cluster units [Ge9(SiPh3)3]? ( 4 ) and [Ge9(SiPh3)2]? ( 5 ), which could be identified by mass spectroscopy. Bis‐ and tris‐silylated species can be synthesized by the respective stoichiometric reactions, and the products were characterized by ESI‐MS and NMR experiments. These clusters show rather different reactivity. The reaction of the tris‐silylated anion 4 with [CuPiPr3Cl] leads to [(CuPiPr3)3Ge9(SiPh3)2]+ as shown from NMR experiments and to [(CuPiPr3)4{Ge9(SiPh3)2}2] ( 6 ), which was characterized by single‐crystal X‐ray diffraction. Compound 6 shows a new type of coordination of the Cu atoms to the silylated Zintl clusters. 相似文献
12.
Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6], and [Ni18S18(PiPr3)6] The reaction of (R)ESiMe3 (R = SiMe3, Mes = C9H11; E = S, Se) with [NiCl2(PPhEt2)2] and [NiCl2(PR3)2] (R = nPr, iPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni5Se4Cl2(PPhEt2)6]·2THF ( 1 ), [Ni12Se12(PnPr3)6]·2THF ( 2 ), and [Ni18S18(PiPr3)6]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses. 相似文献
13.
Synthesis and Dynamic Behaviour of [Rh2(μ-H)3H2(PiPr3)4]+. Contributions to the Reactivity of the Tetrahydridodirhodium Complex [Rh2H4(PiPr3)4] An improved synthesis of [Rh2H4(PiPr3)4] ( 2 ) from [Rh(η3-C3H5)(PiPr3)2] ( 1 ) or [Rh(η3-CH2C6H5)(PiPr3)2] ( 3 ) and H2 is described. Compound 2 reacts with CO or CH3OH to give trans-[RhH(CO)(PiPr3)2] ( 4 ) and with ethene/acetone to yield a mixture of 4 and trans-[RhCH3(CO)(PiPr3)2] ( 5 ). The carbonyl(methyl) complex 5 has also been prepared from trans-[RhCl(CO)(PiPr3)2] ( 6 ) and CH3MgI. Whereas the reaction of 2 with two parts of CF3CO2H leads to [RhH2(η2-O2CCF3) · (PiPr3)2] ( 8 ), treatment of 2 with one equivalent of CF3CO2H in presence of NH4PF6 gives the dinuclear compound [Rh2H5(PiPr3)4]PF6 ( 9a ). The reactions of 2 with HBF4 and [NO]BF4 afford the complexes [Rh2H5(PiPr3)4]BF4 ( 9b ) and trans-[RhF(NO)(PiPr3)2]BF4 ( 11 ), respectively. In solution, the cation [Rh2(μ-H)3H2(PiPr3)4]+ of the compounds 9a and 9b undergoes an intramolecular rearrangement in which the bridging hydrido and the phosphane ligands are involved. 相似文献
14.
Theoretical Study of Pd11Si6 Nanosheet Compounds Including Seven‐Coordinated Si Species and Its Ge Analogues 下载免费PDF全文
下载免费PDF全文 Dr. Yue Chen Yusuke Sunada Prof. Dr. Hideo Nagashima Prof. Dr. Shigeyoshi Sakaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):1076-1087
Nanosheet compounds Pd11(SiiPr)2(SiiPr2)4(CNtBu)10 ( 1 ) and Pd11(SiiPr)2(SiiPr2)4(CNMes)10 ( 2 ), containing two Pd7(SiiPr)(SiiPr2)2(CNR)4 plates (R=tBu or Mes) connected with three common Pd atoms, were investigated with DFT method. All Pd atoms are somewhat positively charged and the electron density is accumulated between the Pd and Si atoms, indicating that a charge transfer (CT) occurs from the Pd to the Si atoms of the SiMe2 and SiMe groups. Negative regions of the Laplacian of the electron density were found between the Pd and Si atoms. A model of a seven‐coordinated Si species, that is, Pd5(Pd?SiMe), is predicted to be a stable pentagonal bipyramidal molecule. Five Pd atoms in the equatorial plane form bonding overlaps with two 3p orbitals of the Si atom. This is a new type of hypervalency. The Ge analogues have geometry and an electronic structure similar to those of the Si compounds. But their formation energies are smaller than those of the Si analogues. The use of the element Si is crucial to synthesize these nanoplate compounds. 相似文献
15.
Three new complexes with phosphanylphosphido ligands, [Cu4{μ2‐P(SiMe3)‐PtBu}4] ( 1 ), [Ag4{μ2‐P(SiMe3)‐PtBu2}4] ( 2 ) and [Cu{η1‐P(SiMe3)‐PiPr2}2]–[Li(Diglyme)2]+ ( 3 ) were synthesized and structurally characterized by X‐ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu2P‐P(SiMe3)Li · 2.7THF with CuCl and [iBu3PAgCl]4, respectively. The X‐ray diffraction analysis revealed that the complexes 1 and 2 present macrocyclic, tetrameric form with Cu4P4 and Ag4P4 core. Complex 3 was prepared in the reaction of CuCl with a different derivative of lithiated diphosphane iPr2P‐P(SiMe3)Li · 2(Diglyme). Surprisingly, the X‐ray analysis of 3 revealed that in this reaction instead of the tetramer the monomeric form, ionic complex [Cu{η1‐P(SiMe3)‐PiPr2}2]–[Li(Diglyme)2]+ was formed. 相似文献
16.
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
17.
Mustafa Tombul R. John Errington Robert A. Coxall William Clegg 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(6):m231-m233
The title compound, bis(borato)dodeca(tert‐butoxo)octadecalithium, [Li18(BO3)2(C4H9O)12], is formulated conveniently as [{(tBuOLi)3(Li3BO3)}2(tBuOLi)6]. A central 12‐membered ring and two outer six‐membered rings are formed by alternating Li+ cations and alkoxide O atoms. Sandwiched between the central ring and each of the outer rings is a planar array of three further Li+ cations surrounding a [BO3]3− anion. Thus, the molecule consists of a cationic [Li18(OtBu)12]6+ cage encapsulating two borate anions. This compound is the first example of a structurally characterized polynuclear lithium borate, and a rare case of a lithium alkoxide cage with nuclearity greater than eight. All the alkoxide ligands are triply bridging, and the lithium ions have trigonal‐planar, trigonal‐pyramidal and fourfold coordination, all with major distortions from regular coordination geometry. 相似文献
18.
The reaction of AlCl3 with Li2PR (R = SiiPr3, SiMeiPr2) in a mixture of heptane and ether yields in the polycyclic compounds [(AlCl)4(μ3‐PR)2(μ‐PR)2(Et2O)2]( 1a : R = SiiPr3; 1b : SiMeiPr2) with a ladder‐shaped Al4P4 core. The coordination sphere of the outer aluminium atoms in these compounds is completed by ether ligands. In contrast, the reaction of AlCl3 with Li2PSiiPr3 in pure heptane yields in the formation of the hexagonal prismatic compound [(AlCl)6(μ3‐PSiiPr3)6]( 2 ). 1 and 2 were characterized by single crystal X‐ray diffraction analysis as well as by 31P{1H} and 27Al NMR spectroscopy. The structure determining effect of the solvent can be rationalized by quantumchemical calculations, which also show that the hexagonal prismatic structure is the most stable of the investigated oligomers in absence of ether. 相似文献
19.
Helmut Werner Ulrich Schmidt Birgit Weberndrfer Carsten D. Brandt 《无机化学与普通化学杂志》2002,628(11):2383-2394
Mono‐ and Dinuclear Rhodium Complexes with Arsino(phosphino)methanes in Different Coordination Modes The cyclooctadiene complex [Rh(η4‐C8H12)(κ2‐tBu2AsCH2PiPr2)](PF6) ( 1a ) reacts with CO and CNtBu to give the substitution products [Rh(L)2(κ2‐tBu2AsCH2PiPr2)](PF6) ( 2 , 3 ). From 1a and Na(acac) in the presence of CO the neutral compound [Rh(κ2‐acac)(CO)(κ‐P‐tBu2AsCH2PiPr2)] ( 4 ) is formed. The reactions of 1a , the corresponding B(ArF)4‐salt 1b and [Rh(η4‐C8H12)(κ2‐iPr2AsCH2PiPr2)](PF6) ( 5 ) with acetonitrile under a H2 atmosphere affords the complexes [Rh(CH3CN)2(κ2‐R2AsCH2PiPr2)]X ( 6a , 6b , 7 ), of which 6a (R = tBu; X = PF6) gives upon treatment with Na(acac‐f6) the bis(chelate) compound [Rh(κ2‐acac‐f6)(κ2‐tBu2AsCH2PiPr2)] ( 8 ). From 8 and CH3I a mixture of two stereoisomers of composition [Rh(CH3)I(κ2‐acac‐f6)(κ2‐tBu2AsCH2PiPr2)] ( 9/10 ) is generated by oxidative addition, and the molecular structure of the racemate 9 has been determined. The reactions of 1a and 5 with CO in the presence of NaCl leads to the formation of the “A‐frame” complexes [Rh2(CO)2(μ‐Cl)(μ‐R2AsCH2PiPr2)2](PF6) ( 11 , 12 ), which have been characterized crystallographically. From 11 and 12 the dinuclear substitution products [Rh2(CO)2(μ‐X)(μ‐R2AsCH2PiPr2)2](PF6) ( 13 ‐ 16 ) are obtained by replacing the bridging chloride for bromide, hydride or hydroxide, respectively. While 12 (R = iPr) reacts with NaI to give the related “A‐frame” complex 18 , treatment of 11 (R = tBu) with NaI yields the mononuclear chelate compound [RhI(CO)(κ2‐tBu2AsCH2PiPr2)] ( 20 ). The reaction of 20 with CH3I affords the acetyl complex [RhI2{C(O)CH3}(κ2‐tBu2AsCH2PiPr2)] ( 21 ) with five‐coordinate rhodium atom. 相似文献
20.
The complex trans-[Rh(CO)(NH3)(PiPr3)2]PF6 (2) was prepared from [(η3-C3H5)Rh(PiPr3)2] (1), NH4PF6 and CO or from 1 and NH4PF6 in presence of an excess of methanol. With an excess of CO, the dicarbonyl and tricarbonyl compounds trans-[Rh(CO)2(PiPr3)2]PF6 (3) and [Rh(CO)3(PiPr3)2]PF6 (4) were obtained. Displacement of one CO ligand in 3 by pyridine and acetone led to the formation of trans-[Rh(CO)(py)PiPr3)2]PF6 (5a) and trans-[Rh(CO) (O=CMe2(PiPr3)2]PF6 (6), respectively. Treatment of 1 with [pyH]BF4 and pyridine gave trans-[Rh(py)2(PiPr3)2]BF4 (7); in presence of H2 the dihydrido complex [RhH2(py)2(PiPr3)2]BF4 (8) was formed. The reaction of 1 with NH4PF6 and ethylene produced trans [Rh(C2H4(NH3(PiPr3)2]PF6(9) whereas with methylvinylketone and acetophenone the octahedral hydridorhodium(III) complexes [RhH(η2-CH=CHC(=O)CH3 (NH3(PiPr3)2]PF6(11) and [RhH(η2-C6H4C(=O)CH3(NH3(Pipr3)2]PF6 (13) were obtained. The synthesis of the cationic vinylidenerhodium(I) compounds trans-[Rh(=C=CHR)(py)(PiPr3)2]BF4 (14–16) and trans-[Rh(=C=CHR)(NH3)(PiPr3) 2]PF6 (17–19) was achieved either on treatment of 1 with [pyH]BF4 or NH4PF6 in presence of 1-alkynes or by ethylene displacement from 9 by HCCR. With tert-butylacetylene as substrate, the alkinyl(hydrido)rhodium(III) complex [RhH(CCtBu)(NH3)(O=CMe2)(PiPr3) 2]PF6 (20) was isolated which in CH2Cl2 solution smoothly reacted to give 19 (R =tBu). The cationic but-2-yne compound trans-[Rh(MeCCMe)(NH3)(Pi Pr3)2]PF6 (21) was prepared from 1, NH4PF6 and C2Me2. The molecular structures of 3 and 14 were determined by X-ray crystallography; in both cases the square-planar coordination around the metal and the trans disposition of the phosphine ligands was confirmed.