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1.
Investigations Concerning the Metallation of the Cyclotetraphosphanes P4(Cme3)3(Sime3), P4(Cme3)2(Sime3)2, and P4(Sime3)4 The reaction of white phosphorus with LiCme3 and me3SiCl yields P4(Sime3)(Cme3)3 1 . With n-buLi this crystalline cyclotetraphosphane forms the crystalline LiP4(Cme3)3. In the same manner, n-buLi, with trans-P4(Sime3)2(Cme3)2 2 to yields LiP4(Sime3)(Cme3)2, which in contrast to LiP4(Cme3)3 decomposes within a few hours yielding P(Sime3)2n-bu 6 , P(Sime3)3 8 , LiP(Sime3)2 9 and also the cyclic compounds P4(Sime3)(Cme3)3 10 , LiP4(Cme3)3 11 and LiP3(Cme3)2 12 . The composition of the product mixture depends on the molar ratio of 2 to LiC4H9. At a molar ratio of 1:1 11 and 12 are not jet observed. At molar ratios of 1:1.5 and 1:2 P(Sime3)3 is not found. The amount of 11 and 12 grows with increasing concentration of n-buLi. On addition of n-buLi the solution of P4(Sime3)4 immediately turns red. Li3P7 and Li2P7(Sime3) (among others) are formed so fast that the first intermediates in the lithiation sequence so far could not be elucidated. These results demonstrate clearly that replacement of two me3Si groups in P4(Sime3)4 by two me3C groups excludes the rearrangement of LiP4(Sime3)(Cme3)2 to a P7-molecule. 相似文献
2.
The Structures of the Heptahetero-Nortricyclenes P7(Sime3)3 and P4(Sime2)3 Tris(trimethylsilyl)heptaphospha-nortricyclene P7(Sime3)3 1 and Hexamethyl-trisila-tetraphospha-nortricyclene P4Si3me6 2 are structural analogons to the hetero-nortricyclenes P and P4S3. 1 crystallizes in the space group P21 with a = 965.7 pm, b = 1746.5 pm, c = 693.3 pm, β = 99.61° and Z = 2 formula units. In the P7 system tge P? P bond lengths differ functionally, namely 221.4 pm in the three-membered ring, 219.2 pm at the ring atoms and 217.9 pm at the bridgehead atom. The P? Si and Si? C bond lengths are 228.8 pm and 187.8 pm respectively. 2 crystallizes in the space group R3 with aR = 1129.3 pm, αR = 50.01° (hexagonal axes: a = 954.7 pm, c = 2956.9 pm) and Z = 2 formula units. In the P4Si3 systems the bond lengths are P? P = 220.2 pm, P? Si = 228.3 pm and 224.7 pm (to the bridgehead atom). The Si? C bond lengths are 187.3 pm. The structures are discussed with related compounds. 相似文献
3.
Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. X. The Influence of the Formation of Complex Compounds on the Reactivity of [(Me3Si)2P]2PH Whereas [(Me3Si)2P]2PH 1 by BuLi is attacked at the PH group to give [(Me3Si)2P]2PLi 2 , the related chromium carbonyl complex (Me3Si)PIV ? 2PIV(H) ? 3PIII(Si? Me3)2 · Cr(CO)4 3 with BuLi yields Li(Me3Si)1PIV ? 2PIV(H) ? 3PIII(SiMe3)2 · Cr(CO)4 4 by cleaving a Si? P bond at the chromium substituted 1P atom. Dissolved in ether, 4 is stable for a longer time, while under comparable conditions 2 forms Li3P7 which is not obtained from 4 . MeOH in 3 cleaves selectively the Me3Si groups from the complex substituted P atom yielding (Me3Si)(H)1PIV ? 2PIV(H) ? 3PIII(SiMe3)2 · Cr(CO)4 5 and HPIV ? 2PIV(H) ? 3PIII(SiMe3)2Cr(CO)4 6. 5 and 6 seem to be stable in contrast to the uncoordinated triphosphanes which are not known. 相似文献
4.
Harald Krautscheid Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(4):675-678
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η2‐{tBu–P=P–SiMe3}Pt(PR3)2] from (Me3Si)tBuP–P=P(Me)tBu2 and [η2‐{C2H4}Pt(PR3)2] (Me3Si)tBuP–P = P(Me)tBu2 reacts with [η2‐{C2H4}Pt(PR3)2] yielding [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]. However, there is no indication for an isomer which would be the analogue to the well known [η2‐{tBu2P–P}Pt(PPh3)2]. The syntheses and NMR data of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] and [η2‐{tBu–P=P–SiMe3}Pt(PMe3)2] as well as the results of the single crystal structure determination of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] are reported. 相似文献
5.
Investigations on Lithiation and Substitution of HP[Si(t-Bu)2]2PH HP[Si(t-Bu)2]2PH 1 is monolithiated by reaction with LiPH2 · DME or LiBu in toluene. The crystalline compound HP[Si(t-Bu)2]2PLi · 2 DME 2 can be isolated in DME. Reaction of 2 with Me2SiCl2 leads to HP[Si(t-Bu)2]2P? SiMe2Cl 4 , ClMe2Si? P[Si(t-Bu)2]2P? SiMe2Cl 5 , HP[Si(t-Bu)2]2P? SiMe2? P[Si(t-Bu)2] 2PH 6 . Isomerization by Li/H migration between 4 and 2 leads to the formation of 5 . Reaction of Li(t-Bu) with 1 or 2 yields LiP[Si(t-Bu)2]2PLi 3 by further lithiation. 3 could not be obtained purely, only in a mixture with 2 . These compounds favourably generate with t-BuPCl2 in hexane Cl(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)Cl 9 , in THF HP[Si(t-Bu)2]2P? P(t-Bu)? P[Si(t-Bu)2]2 PH 12 (main product), 9 , H(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)Cl 10 , H(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)H 11 as well as HP[Si(t-Bu)2]2P? P(t-Bu)H 13 and HP[Si(t-Bu)2]2P? P(t-Bu)2 14 . 相似文献
6.
Reactions of [(me3Si)2P]2PLi with Chlorophosphanes [(me3Si)2P]2PLi 1 with (C6H5)2PCl yields only a small amount of the expected [(me3Si)2P]2P–P(C6H5)2 2 ; the main products are (me3Si)2P–P(C6H5)2 3 and (C6H5)2P–P(C6H5)2 4 besides some (me3Si)3P 5 and (C6H5)2P–Sime3 6. 3 and 4 result from the metallation of (C6H5)2PCl by 1 t-buPCl2 and 1 form the P3-ring (me3Si)(me3C)P3[P(Sime3)2] 9 as main product besides some [(me3Si)2P]2P–Sime3 7 and 5. 9 is afforded by elimination of me3SiCl, from the initially formed unstable [(me3Si)2P]2P–P(Cl)Cme3 10 . Similarly 1 and PCl3 yield mainly the P3-ring (me3Si)(Cl)P3 · [P(Sime3)2] 11 due to elimination of me3SiCl from [(me3Si)2P]2P–PCl2. 相似文献
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8.
Hexamethyl-trisila-tetraphospha-nortricyclene, P4 Sime23 Reaction of white phosphorus with Na/K alloy and subsequent treatment with me2SiCl2 (me = CH3) yields crystalline P4(Sime2)3 (m. p. 159–160°C) along with polymeric silylphosphanes. The structure is derived from 31P-n.m.r.and mass spectra and turns out to be analogous to P4S3. 相似文献
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10.
Preparation, Structures, and Properties of Tris-hexamethyl-trisila-tetraphospha-nortricyclene-bis-chromiumtricarbonyl [P4(Sime2)3]3[Cr(CO)3]2 Hexamethyl-trisila-tetraphospha-nortricyclene P4(Sime2)3 1 reacts with C6H6Cr(CO)3 or (CHT)Cr(CO)3 (CHT ? Cycloheptatriene) under formation of [P4(Sime2)3]3[Cr(CO)3]2 3 (red crystals), in which each of the Cr atoms is attached to one P atom of a P3 ring of the three molecules 1 . 3 can also be prepared by heating a solution of P4(Sime2)3Cr(CO)5 in benzene or THF up to 120–1307deg;C. The compound 3 crystallizes in an orthorhombic and a hexagonal form, the latter being stabilized by one mole toluene. As revealed by single crystal investigations, the symmetry ¯6, distances and angles are nearly unchanged. The o-form corresponds to a face centered cubic packing of the molecules, whereas the h-form is hexagonal close packed. 相似文献
11.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVIII. Syntheses and Structures of [{η2‐tBu2P–P=P–PtBu2}Pt(PR3)2] tBu2P–P=P(Me)tBu2 reacts with [{η2‐C2H4} · Pt(PR3)2] as well as with [{η2‐tBu2P–P}Pt(PR3)2] yielding [{η2‐tBu2P–P=P–PtBu2}Pt(PR3)2]; PR3 = PMe3 3 a , PEtPh2 3 b , 1/2 dppe 3 c , PPh3 3 d , P(p‐Tol)3 3 e . All compounds are characterized by 1H and 31P NMR spectra, for 3 b and 3 d also crystal structure determinations were performed. 3 b crystallizes in the triclinic space group P1 (No. 2) with a = 1212.58(7), b = 1430.74(8), c = 1629.34(11) pm, α = 77.321(6), β = 70.469(5), γ = 87.312(6)°. 3 d crystallizes in the triclinic space group P1 (No. 2) with a = 1122.60(9), b = 1355.88(11), c = 2025.11(14) pm, α = 83.824(9), β = 82.498(9), γ = 67.214(8)°. 相似文献
12.
[t-Bu2P]3P7 and (t-Bu2Sb)3P7, as well as Investigations on the Formation of Heptaphosphanes (3) Containing PMe2, PF2, and P(CF3)2 Groups Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu2P)3P7 1 obtained by reacting Li3P7 · 3 DME with t-Bu2PF forms yellow crystals. (t-Bu2Sb)3P7 2 produced similarly from t-Bu2SbCl and Li3P7 · 3 DME didn't form crystals; it decomposes in a solution of toluene above ?10°C. Both compounds were identified by their 31P{1H} NMR spectra, and 1 also by elemental analysis and single crystal structure determination (space group) P21/a, a = 1 712.0(9) pm, b = 1 105.1(7) pm, c = 1 854.0(10) pm, β = 94.96(4)°, Z = 4 formula units in the elementary cell). Attempts to synthesize (Me2P)3P7 3 , (F2P)3P7 4 and [(F3C)2P]3P7 5 failed as dialkylchlorophosphanes as Me2PCl e. g. with Li3P7 · 3 DME react under Li/Cl exchange, dialkylfluorophosphanes (except t-Bu2PF) disproportionate, and neither PF3 nor (F3C)2PBr with Li3P7 · 3 DME give the desired products 4 or 5 , resp. 相似文献
13.
Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(8):1767-1770
The Reactions of tBu2P–P=P(Me)tBu2 and (Me3Si)tBuP–P=P(Me)tBu2 with PR3 tBu2P–P=P(Me)tBu2 ( 1 ) reacts at 20 °C with PMe3, PEt3, P(c‐Hex)3, P(p‐Tol)3, PPh2Me, PPh2Et, PPhEt2, PPh2iPr, PPh3 and P(NEt2)3 yielding tBu2P–P=PR3 and tBu2PMe; however, PtBu3, PtBu2(SiMe3) and tBu2PCl don't. tBu2PH and 1 form tBu2P–PH–PtBu2 which yields tBu2P–P=PEt3 when treated with PEt3. Ph2PH, tBuPH2, PH3, Ph2PCl and EtOH don't substitute the tBu2PMe group in 1 , instead, the molecule is decomposed. With PEt3, (Me3Si)tBuP–P=P(Me)tBu2 forms (Me3Si)tBuP–P=PEt3. The compounds tBu2P–P=PR3 decompose at 20 °C to different degrees giving P‐rich consecutive products of the phosphinophosphinidene. 相似文献
14.
Synthesis and Structures of Novel Ring Compounds of Bismuth with Tris(trimethylsilyl)silyl and ‐stannyl Substituents – [(Me3Si)3Si]4Bi4 and [(Me3Si)3Sn]6Bi8 A bicyclo[3.3.0]octane‐like core consisting of eight bismuth atoms is found in the novel octabismuthane Bi8[Sn(SiMe3)3]6. It is prepared like Bi4[Si(SiMe3)3]4 by reduction of BiBr3 with Li(thf)3E(SiMe3)3 (E = Si, Sn) together with (Me3Si)6E2. Both bismuth ring compounds have been characterized by single crystal X‐ray crystallography. 相似文献
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16.
Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII Carbonyl Complexes of the Heptaphosphane(3) iPr2(Me3Si)P7 From the reaction of iPr2(Me3Si)P7 1 with one equivalent of Cr(CO)5THF the yellow products iPr2(H)P7[Cr(CO)5] 2 and iPr2(Me3Si)P7[Cr(CO)5] 3 were isolated by column chromatography on silicagel. The P? H group in 2 results from a cleavage of the P? SiMe3 bond during chromatography. The Cr(CO)5 group in 2 is linked to an iPr? Pe atom, in 3 to the Me3Si? Pe atom of the P7 skeleton. The substituents do not force the formation of a single isomer; nevertheless 3 ist considerably favoured as compared to 2 . From the reaction of 1 with 2 equivalents of Cr(CO)5THF the yellow iPr2(H)P7[Cr(CO)5]2 4 was isolated bearing one Cr(CO)5 group at an iPr? Pe atom, the other one at a Pb atom of the P7 skeleton. Compound 3 yields with Cr(CO)4NBD the red iPr2(Me3Si)P7[Cr(CO)5][Cr(CO)4] 5 . Three isomers of 5 appear. Two Pe atoms of 5 are bridged by the Cr(CO)4 group, the third Pe atom is linked to the Cr(CO)5 ligand. iPr2(H)P7[Fe(CO)4] was isolated from the reaction of 1 with Fe2(CO)9. 31P NMR and MS data are reported. 相似文献
17.
tBu2P–PLi–PtBu2·2THF reacts with [cis‐(Et3P)2MCl2] (M = Ni, Pd) yielding [(1,2‐η‐tBu2P=P–PtBu2)Ni(PEt3)Cl] and [(1,2‐η‐tBu2P=P–PtBu2)Pd(PEt3)Cl], respectively. tBu2P– PLi–PtBu2 undergoes an oxidation process and the tBu2P–P–PtBu2 ligand adopts in the products the structure of a side‐on bonded 1,1‐di‐tert‐butyl‐2‐(di‐tert‐butylphosphino)diphosphenium cation with a short P–P bond. Surprisingly, the reaction of tBu2P–PLi–PtBu2·2THF with [cis‐(Et3P)2PtCl2] does not yield [(1,2‐η‐tBu2P=P–PtBu2)Pt(PEt3)Cl]. 相似文献
18.
Transition Metal Complexes of the Hexamethyl-trisila-tetraphospha-nortricyclene P4 (Sime 2) 3 P4(Sime2)3 1 reacts with Mo(CO)6, Cr(CO)5THF, and Mn(η-C5H5)(CO)2THF to give crystalline complexes in which 1 functions as a monodentate ligand. In each compound one phophorus atom of the cyclotriphosphane ring coordinates to the metal atom. Using Mn(η-C5H5)(CO)2THF, two different P atoms of the P3 Cr(CO)4 norbornadiene and 1 react, yielding the dimeric, red, crystalline compound (CO) 4Cr[μ-P4(Sime2)3]2Cr(CO)4. In this complex the two molecules of 1 are both bonded by two P atoms of the P 3 ring to the two Cr(CO)4 Units, forming a six-memered (CrP2)2ring. 相似文献
19.
Ewald Sattler Harald Krautscheid Eberhard Matern Gerhard Fritz Ilona Kovcs 《无机化学与普通化学杂志》2001,627(2):186-193
Formation and Reactions of the CH2Li‐Derivatives of tBu2P–P=P(CH3)tBu2 and (Me3Si)tBuP–P=P(CH3)tBu2 With nBuLi, (Me3Si)tBuP–P=P(CH3)tBu2 ( 1 ) and tBu2P–P=P(CH3)tBu2 ( 2 ) yield (Me3Si)tBuP–P=P(CH2Li)tBu2 ( 3 ) and tBu2P–P=P(CH2Li)tBu2 ( 4 ), wich react with Me3SiCl to give (Me3Si)tBuP–P=P(CH2–SiMe3)tBu2 ( 5 ) and tBu2P–P=P(CH2–SiMe3)tBu2 ( 6 ), respectively. With tBu2P–P(SiMe3)–PtBuCl ( 7 ), compound 3 forms 5 as well as the cyclic products [H2C–P(tBu)2=P–P(tBu)–PtBu] ( 8 ) and [H2C–P(tBu)2=P–P(PtBu2)–P(tBu)] ( 9 ). Also 3 forms 8 with tBuPCl2. The cleavage of the Me3Si–P‐bond in 1 by means of C2Cl6 or N‐bromo‐succinimide yields (Cl)tBuP–P=P(CH3)tBu2 ( 10 ) or (Br)tBuP–P=P(CH3)tBu2 ( 11 ), resp. With LiP(SiMe3)2, 10 forms (Me3Si)2P–P(tBu)–P=P(CH3)tBu2 ( 12 ), and Et2P–P(tBu)–P=P(CH3)tBu2 ( 13 ) with LiPEt2. All compounds are characterized by 31P NMR Data and mass spectra; the ylide 5 and the THF adduct of 4 additionally by X‐ray structure analyses. 相似文献
20.
Helmut Goesmann Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(6):1181-1184
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIII. Reactions of tBu2P–P=P(Me)tBu2 with (Et3P)2NiCl2 and [{η2‐C2H4}Ni(PEt3)2] tBu2P–P=P(Me)tBu2 ( 1 ) forms with (Et3P)2NiCl2 ( 2 ) and Na(Nph) the [μ‐(1,3 : 2,3‐η‐tBu2P4tBu2){Ni(PEt3)Cl}2] ( 3 ) as main product. Using Na/Hg instead as reducing agent the Ni0 compounds [{η2‐tBu2P–P}Ni(PEt3)2] ( 4 ), [{η2‐tBu2P–P=P–PtBu2}Ni(PEt3)2] ( 5 ) and [(Et3P)Ni(μ‐PtBu2)]2 ( 6 ) with four‐membered Ni2P2 ring result. [{η2‐C2H4}Ni(PEt3)2] yields with 1 also 4 . The compounds were characterized by 1H and 31P{1H} NMR investigations and 3 also by a single crystal X‐ray analysis. It crystallizes triclinic in the space group P 1 with a = 1129.4(2), b = 1256.8(3), c = 1569.5(3) pm, α = 72.44(3)°, β = 70.52(3)° and γ = 74.20(3)°. 相似文献