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1.
Reaction Behaviour of Copper(I) and Copper(II) Salts Towards P(C6H4CH2NMe2‐2)3 ‐ the Solid‐State Structures of {[P(C6H4CH2NMe2‐2)3]CuOClO3}ClO4, {[P(C6H4CH2NMe2‐2)3]Cu}ClO4, [P(C6H4CH2NMe2‐2)3]CuONO2 and [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐2)]CuONO2 The reaction behaviour of P(C6H4CH2NMe2‐2)3 ( 1 ) towards different copper(II) and copper(I) salts of the type CuX2 ( 2a : X = BF4, 2b : X = PF6, 2c : X = ClO4, 2d : X = NO3, 2e : X = Cl, 2f : X = Br, 13 : X = O2CMe) and CuX ( 5a : X = ClO4, 5b : X = NO3, 5c : X = Cl, 5d : X = Br) is discussed. Depending on X, the transition metal complexes [P(C6H4CH2NMe2‐2)3Cu]X2 ( 3a : X = BF4, 3b : X = PF6), {[P(C6H4CH2NMe2‐2)3]CuX}X ( 4 : X = ClO4, 11a : X = Cl, 11b : X = Br, 14 : X = O2CMe), {[P(C6H4CH2NMe2‐2)3]Cu}ClO4 ( 6 ), [P(C6H4CH2NMe2‐2)3]CuX ( 7a : X = Cl, 7b : X = Br, 10 : X = ONO2), [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐2)]CuONO2 ( 9 ) and [P(C6H4CH2NMe2‐2)3]CuCl}CuCl2 ( 12 ) are accessible. While in 3a , 3b and 6 the phosphane 1 preferentially acts as tetrapodale ligand, in all other species only the phosphorus atom and two of the three C6H4CH2NMe2 side‐arms are datively‐bound to the appropriate copper ion. In solution a dynamic behaviour of the latter species is observed. Due to the coordination ability of X in 3a , 3b and 6 non‐coordinating anions X are present. However, in 4 one of the two perchlorate ions forms a dative oxygen‐copper bond and the second perchlorate ion acts as counter ion to {[P(C6H4CH2NMe2‐2)3]CuOClO3}+. In 7 , 9 and 10 the fragments X (X = Cl, Br, ONO2) form a σ‐bond with the copper(I) ion. The acetate moiety in 14 acts as chelating ligand as it could be shown by IR‐spectroscopic studies. All newly synthesised cationic and neutral copper(I) and copper(II) complexes are representing stable species. Redox processes are involved in the formation of 9 and 12 by reacting 1 with 2 . The solid‐state structures of 4 , 6 , 9 and 10 are reported. In the latter complexes the copper(II) ( 4 ) or copper(I) ion ( 6 , 9 , 10 ) possesses the coordination number 4. This is achieved by the formation of a phosphorus‐ and two nitrogen‐copper‐ ( 4 , 9 , 10 ) or three ( 6 ) nitrogen‐copper dative bonds and a coordinating ( 4 ) or σ‐binding ( 9 , 10 ) ligand X. In 6 all three nitrogen and the phosphorus atoms are coordinatively bound to copper, while X acts as non‐coordinating counter‐ion. Based on this, the respective copper ion occupies a distorted tetrahedral coordination sphere. While in 4 and 10 a free, neutral Me2NCH2 side‐arm is present, which rapidly exchanges in solution with the coordinatively‐bound Me2NCH2 fragments, this unit is protonated in 10 . NO3 acts as counter ion to the CH2NMe2H+ moiety. In all structural characterized complexes 6‐membered boat‐like CuPNC3 cycles are present.  相似文献   

2.
Synthesis of Monomeric T‐Shaped Silver(I) Halide Complexes – Crystal Structure Analysis of [P(C6H4CH2NMe2‐2)3]AgBr Treatment of the tetrapodal phosphane P(C6H4CH2NMe2‐2)3 ( 1 ) with equimolar amounts of the silver(I) halides AgX ( 2 a : X = Cl, 2 b : X = Br) produces in tetrahydrofuran at 25 °C the monomeric silver(I) complexes [P(C6H4CH2NMe2‐2)3]AgX with planar coordination at the Ag atoms ( 3 a : X = Cl, 3 b : X = Br) in excellent yields. From complex 3 b a single X‐ray crystal structure analysis was carried out. Mononuclear 3 b crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.504(6), b = 11.034(3), c = 17.604(5) Å, β = 102.86(4)°; V = 2746.6(16) Å3; Z = 4; 2953 observed unique reflections, R1 = 0.0805. Complex 3 b consists of monomeric sub‐units with a planar T‐shaped arrangement formed by the atoms Ag1, N1, P1 as well as Br1, whereby the P1–Ag1–Br1 array is almost linear orientated.  相似文献   

3.
From the reaction of 1‐HOCPh2‐2‐NMe2C6H4 ( 1 ), 1‐HOC(C6H11)2‐2‐NMe2C6H4 ( 2 ) and 1‐HOCPh2CH2‐2‐NMe2C6H4 ( 3 ) with n‐BuLi in diethyl ether, the solvent‐free chelated dimethylamino lithium alkoxides [1‐LiOCPh2‐2‐NMe2C6H4]2 ( 4 ), [1‐LiOC(C6H11)2‐2‐NMe2C6H4]2 ( 5 ) and [1‐LiOCPh2CH2‐2‐NMe2C6H4]2 ( 6 ) were obtained. The lithium alkoxides 4 – 6 were characterized by 1H, 7Li, and 13C NMR spectroscopy. Crystal structure determinations of 5 and 6 were carried out. Compounds 5 and 6 are examples of structurally characterized solvent‐free chelated dimethylamino lithium alkoxides and 6 is a rare example of this type containing a seven‐membered ring. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

4.
Treatment of GaCl3 with one equiv of Li[NC4H3(CH2NMe2)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl3‐n[NC4H3(CH2NMe2)‐2]n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR2[NC4H3(CH2NMe2)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature 1H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by 1H and 13C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography.  相似文献   

5.
The title compounds 3‐5 are accessible by treatment of P(C6H4CH2NMe2)3( 1 ) with CuX ( 2a : X = Cl, 2b : X = Br, 2c : X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1 with equimolar amounts of 2a affords the copper(I) chloride [P(C6H4CH2NMe2)3]CuCl ( 3 ). With a further equivalent of 2a homobimetallic [P(C6H4CH2NMe2)3]Cu2Cl2 ( 4 ) is formed, which also can be synthesized by the reaction of 1 with two equivalents of 2a. Complex 3 reacts with CuX (X = Br, I)to afford [P(C6H4CH2NMe2)3]Cu2ClX ( 5a : X = Br; 5b : X = I) in which mixed halides are present. The newly synthesized complexes 3‐5 were characterized by elemental analyses, by their IR‐, 1H‐, 13C{1H}‐ and 31P{1H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3 and 4 are reported. Mononuclear 3 crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å 3 and Z = 4 with 4053 observed unique reflections; R1 = 0.0314. The crystal structure of 3 consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4 crystallizes in the monoclinic space group P21/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; 3 and Z = 4 with 9021 observed unique reflections; R1 = 0.0480. In 4 one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu2Cl2 segment resembles to a building block which is set up by a contact ion pair consisting of Cu+ and [CuCl2] , respectively.  相似文献   

6.
Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C6H4C(O)N(H)P(O)X2, X = NH‐C(CH3)3 ( 1 ), NH‐CH2‐CH=CH2 ( 2 ), NH‐CH2C6H5 ( 3 ), N(CH3)(C6H5) ( 4 ), NH‐CH(CH3)(C6H5) ( 5 ) were synthesized and characterized by 1H, 13C, 31P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. 1H and 13C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. 13C NMR spectrum of compound 4 shows that 2J(P,Caliphatic) coupling constant for CH2 group is greater than for CH3 in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C6H4C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C6H4CN+ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.  相似文献   

7.
N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF3)2BNMe2 ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C6H5 ( 4 ), and p‐CH3C6H4 ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF3)2B‐NMe2‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C6H5 ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.  相似文献   

8.
Hydrolysereak‐Syntheses, Properties and Molecular Structures of the Heterobimetalorganics of the four‐valued Germanium with the 2‐(Dimethylaminomethyl)ferrocenyl Ligand FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)‐2] The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, FcNLi, reacts with germanium(IV) chloride, GeCl4, under the formation of heterobimetallic germanium(IV) organyls (FcN)nGeCl4‐n (n = 2 ( 1 ), 3 ( 2 )). The heterobimetallic organogermanol (FcN)3GeOH ( 3 ) is formed at hydrolysis of 2 . A detailed characterization of the defined compounds 1 — 3 was carried out by single crystal X‐ray analyses, NMR‐ and mass‐spectrometry.  相似文献   

9.
Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)2SnCl2 (FcN, N: (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}) The heterobimetallic title compound [(FcN, N)2SnCl2] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl4 in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P21/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1obs· = 0.051, wR2obs· = 0.136.  相似文献   

10.
Some new phosphoramidates were synthesized and characterized by 1H, 13C, 31P NMR, IR spectroscopy and elemental analysis. The structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 ( 1 ) and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2 ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. 13C NMR spectra were used for study of 2J(P,C) and 3J(P,C) coupling constants that were showed in the molecules containing N(C2H5)2 and N(C2H5)(CH2C6H5) moieties, 2J(P,C)>3J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC4H8. 2J(P,C) for N(C2H5)2 moiety and in NC4H8 are nearly the same, but 3J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH2R)(CH2C6H5)]2, 2J(P,CH2)benzylic>2J(P,CH2)aliphatic, in an agreement with our previous study.  相似文献   

11.
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   

12.
Syntheses and characteristics of the heterobimetalorganics of the silicon with the 2‐(dimethylaminomethyl)ferrocenyl ligand FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)] The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, LiFcN, reacts with silicon(IV)‐chlorid, SiCl4, under the formation of heterobimetallic silicon(IV) organyl [(FcN)3SiCl] ( 1 ). The heterobimetallic organosilanol [(FcN)3SiOH] ( 2 ) is formed at hydrolysis of 1 . A detailed characterization of the defined compounds 1 and 2 was carried out by NMR‐ rsp. mass‐spectrometry and by crystal X‐ray analysis of 2 .  相似文献   

13.
Trimethylamine‐bis(trifluoromethyl)boranes R(CF3)2B · NMe3 (R = cis/trans‐CF3CF=CF ( 1/2 ), HC≡C ( 3 ), H2C=CH ( 4 ), C2H5 ( 5 ), C6H5CH2 ( 6 ), C6F5 ( 7 ), C6H5 ( 8 )) react with NEt3 × 3 HF depending on the nature of R at 155–200 °C under replacement of the trimethylamine ligand to form the corresponding fluoro‐bis(trifluoromethyl)borates [R(CF3)2BF] ( 1 a/2 a – 8 a ). The structures of 7 , K[C6H5CH2(CF3)2BF] ( K‐6 a ), and K[C6H5(CF3)2BF] ( K‐8 a ) have been investigated by single‐crystal X‐ray diffraction. In 7 the CF3 groups make short repulsive contacts with NMe3 and C6F5 entities – the B–CF3 bonds being unusually long. The B–F bond lengths of K‐6 a and K‐8 a (1.446(3) and 1.452(2) Å, respectively) are long for a fluoroborate.  相似文献   

14.
Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with nBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr3 and AuCl · PPh3 the heterobimetallic organo derivatives (FcN,N)AlBr2 ( 3 ), (FcN,N)Au · PPh3 ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.  相似文献   

15.
The reaction of 1‐NHPhCHPh‐2‐NMe2C6H4 ( 1 ) and 1‐NHPhCHPhCH2‐2‐NMe2C6H4 ( 2 ) with n‐BuLi in diethyl ether gave the solvent‐free chelated dimethylamino lithium amides [1‐LiNPhCHPh‐2‐NMe2C6H4]2 ( 3 ) and [1‐LiNPhCHPhCH2‐2‐NMe2C6H4]2 ( 4 ). The lithium amides 3 and 4 were characterized by 1H, 7Li, and 13C NMR spectroscopy. A crystal structure determination was carried out on 4 , which is the first example of a structurally characterized solvent‐free dimeric chelated dimethylamino lithium arylamide with three‐coordinate lithium centers that contains a seven‐membered chelate ring. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

16.
The Reactions of CH2=P(NMe2)3 with Fe(CO)5, Cr(CO)6, and CS2; Molecular Structures of [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3], and (CO)4Fe=C(OMe)CH=P(NMe2)3 The ylide CH2=P(NMe2)3 ( 1 ) reacts with several binary transition metal carbonyls M(CO)x to produce the corresponding salt like compounds [MeP(NMe2)3][(CO)x–1MC(O)CH=P(NMe2)3] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS2 leads to the salt [MeP(NMe2)3][SC(S)CH=P(NMe2)3] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe2)3]2[Fe2(CO)8] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO3CF3 produces the related carbene complexes (CO)x–1M=C(OMe)CH=P(NMe2)3 ( 5 ) and ( 6 ); the reaction of 3 with Me3SiCl results in the formation of the carbene complex (CO)4Fe=C(OSiMe3)CH=P(NMe2)3 ( 7 ). 4 crystallizes in the space group P212121 (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P21/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (1H, 13C, 31P) and IR spectroscopy.  相似文献   

17.
(R)‐[1‐(Dimethylamino)ethyl]benzene reacts with nBuLi in a 1:1 molar ratio in pentane to quantitatively yield a unique hetero‐aggregate ( 2 a ) containing the lithiated arene, unreacted nBuLi, and the complexed parent arene in a 1:1:1 ratio. As a model compound, [Li4(C6H4CH(Me)NMe2‐2)2(nBu)2] ( 2 b ) was prepared from the quantitative redistribution reaction of the parent lithiated arene Li(C6H4CH(Me)NMe2‐2) with nBuLi in a 1:1 molar ratio. The mono‐Et2O adduct [Li4(C6H4CH(Me)NMe2‐2)2(nBu)2(OEt2)] ( 2 c ) and the bis‐Et2O adduct [Li4(C6H4CH(Me)NMe2‐2)2(nBu)2(OEt2)2] ( 2 d ) were obtained by re‐crystallization of 2 b from pentane/Et2O and pure Et2O, respectively. The single‐crystal X‐ray structure determinations of 2 b – d show that the overall structural motifs of all three derivatives are closely related. They are all tetranuclear Li aggregates in which the four Li atoms are arranged in an almost regular tetrahedron. These structures can be described as consisting of two linked dimeric units: one Li2Ar2 dimer and a hypothetical Li2nBu2 dimer. The stereochemical aspects of the chiral Li2Ar2 fragment are discussed. The structures as observed in the solid state are apparently retained in solution as revealed by a combination of cryoscopy and 1H, 13C, and 6Li NMR spectroscopy.  相似文献   

18.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVII [1] [Co(g5‐Me5C5)(g3tBu2PPCH–CH3)] from [Co(g5‐Me5C5)(g2‐C2H4)2] and tBu2P–P=P(Me)tBu2 [Co(η5‐Me5C5)(η3tBu2PPCH–CH3)] 1 is formed in the reaction of [Co(η5‐Me5C5)(η2‐C2H4)2] 2 with tBu2P–P 4 (generated from tBu2P–P=P(Me)tBu2 3 ) by elimination of one C2H4 ligand and coupling of the phosphinophosphinidene with the second one. The structure of 1 is proven by 31P, 13C, 1H NMR spectra and the X‐ray structure analysis. Within the ligand tBu2P1P2C1H–CH3 in 1 , the angle P1–P2–C1 amounts to 90°. The Co, P1, P2, C1 atoms in 1 look like a „butterfly”︁. The reaction of 2 with a mixture of tBu2P–P=P(Me)tBu2 3 and tBu–C?P 5 yields [Co(η5‐Me5C5){η4‐(tBuCP)2}] 6 and 1 . While 6 is spontaneously formed, 1 appears only after complete consumption of 5 .  相似文献   

19.
Oligophosphanide Anions: Syntheses and Molecular Structures of [K2(PMDETA)2(P4Ph4)], [K2(PMDETA)(P4tBu4)]2 and [K(PMDETA)(THF){cyclo‐(P5tBu4)}] (PMDETA = NMe(CH2CH2NMe2)2) The alkali metal tetraphosphanediides [K2(PMDETA)2(P4Ph4)] ( 1 ) and [K2(PMDETA)(P4tBu4)]2 ( 2 ) [PMDETA = NMe(CH2CH2NMe2)2] were synthesized via reaction of PhPCl2 or tBuPCl2 with 2.5 equiv. potassium and characterized by X‐ray crystallography and 31P NMR spectroscopy. As in other ion contact complexes of the type M2(P4R4) (M = alkali metal) the solid‐state structures are retained in solution. While 1 could be prepared in comparatively good yield (54 %), 2 was only isolated in very modest yield and with low purity as [K(PMDETA)(THF){cyclo‐(P5tBu4)}] ( 3 ) was formed as a side product in this case. 3 was also characterized by X‐ray crystallography and 31P NMR spectroscopy.  相似文献   

20.
The crystal and molecular structures of the title compound, 3‐bromo‐3‐(di­benzyl­phenyl­phospho­nio)‐2,2‐di­phenyl‐5‐trifluoromethyl‐1H‐benzo­[e][1,2]­phosphanickelepine, [NiBr(C22H17F3P)(C20H19P)], which was obtained as the major regioisomer from insertion of HCCCF3 into the Ni—C bond of the five‐membered phosphanickelacycle [NiBr(o‐C6H4CH2PPh2‐κ2C,P){PPh(CH2Ph)2}], have been determined. Principal geometric data include the Ni—X bond lengths Ni—Br 2.3343 (4) Å, Ni—P 2.1867 (7) and 2.2094 (7) Å, and Ni—C 1.882 (3) Å, and the two trans angles P—Ni—P 171.55 (3)° and Br—Ni—C 176.88 (9)°.  相似文献   

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