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1.
Reaction of (CH3NPF3)2 with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH3N)4P3F7, the new spiro-isomer F3P(CH3N)2PF(CH3N)2PF3 and the spiro-compound F3P(CH3N)2PF(CH3N)2PF(CH3N)2PF3, an isomer of the known compound (CH3N)6P4F8.  相似文献   

2.
Syntheses, Structure Determination and Reactions of Phosphine Substituted Derivatives of Fe3(CO)9(μ3-CF)2 Photolysis of Fe3(CO)9(μ3-CF)2 1 in the presence of acetonitrile 2a or benzoenitrile 2b results in the substitution of a single carbonyl ligand by a nitrile ligand yielding Fe3(CO)8(CH3CN)(μ3-CF)2 3a and Fe3(CO)8(C6H5CN)(μ3-CF)2 3b, respectively. The acetonitrile ligand in 3a can be easily replaced by trimethyl-phosphine 4a or triphenylphosphine 4b . The monosubstituted compounds Fe3(CO)8(PR3)(μ3-CF)25, R = CH3 a, R = C6H5, b are obtained as major products besides a small amount of the disubsituted products Fe3(CO)7(PR3)2(μ3-CF)2 6. The structure of 5a has been elucidated by a single crystal X-ray structure determination. Thermal ligand substitution in 1, however, results in the formation of a mixture of mono-, disubstituted, and trisubstituted products, in which 6b is the major product for diphenylphosphine. 5a reacts with ethyne 7 forming a phosphine substituted diferra-allyl-cluster Fe3(CO)7(PR3)(μ3-CF)(μ3? CF? CH? CH) 8. The structure of one isomere of 8 has been determinated by X-ray crystallography.  相似文献   

3.
Xenon trioxide (XeO3) forms adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone by coordination of the ligand oxygen atoms to the XeVI atom of XeO3. The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction, and Raman spectroscopy. Unlike solid XeO3, which detonates when mechanically or thermally shocked, solid (C5H5NO)3(XeO3)2, [(C6H5)3PO]2XeO3, and [(CH3)2SO]3(XeO3)2 are insensitive to mechanical shock. The [(CH3)2SO]3(XeO3)2 adduct slowly decomposes over several days to (CH3)2SO2, Xe, and O2. All three complexes undergo rapid deflagration when ignited by a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are room-temperature stable and the [(CH3)2CO]3XeO3 complex dissociates at room temperature to form a stable solution of XeO3 in acetone. The xenon coordination sphere of [(C6H5)3PO]2XeO3, a distorted square-pyramid, provides the first example of a five-coordinate XeO3 complex with only two Xe- - -O adduct bonds. The xenon coordination spheres of the remaining adducts are distorted octahedra, comprised of three Xe- - -O secondary bonds that are approximately trans to the primary Xe−O bonds of XeO3. Quantum-chemical calculations were used to assess the nature of the Xe- - -O adduct bonds, which are described as predominantly electrostatic bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the electrophilic xenon atoms.  相似文献   

4.
The combination of RbB3O4F2 and NaF generates a new member of fluorooxoborates, NaRbB3O4F3, with a wide transparency range from the IR to DUV region. NaRbB3O4F3 shows a three-dimensional (3D) structure composed of 1D [B3O4F3]∞ chains, [NaO3F3] and [RbO5F5] polyhedra. The structural evolution from NaRbB3O4F3 to RbB3O4F2, as well as the structural comparison between NaRbB3O4F3 and its identical stoichiometry compound, Li2B3O4F3 were discussed in detail. The IR spectrum verifies its structural validity. The spectral measurement shows that the reflectance has no obvious change in the range of 175–300 nm, and its cutoff edge is below 175 nm. In addition, theoretical calculations are carried out to understand its electronic structure and optical properties.  相似文献   

5.
There have been recent reports on the formation of single‐halide perovskites, CH3NH3PbX3 (X=Cl, Br, I), by means of vapor‐assisted solution processing. Herein, the successful formation of mixed‐halide perovskites (CH3NH3PbI3?xXx) by means of a vapor‐assisted solution method at ambient atmosphere is reported. The perovskite films are synthesized by exposing PbI2 film to CH3NH3X (X=I, Br, or Cl) vapor. The prepared perovskite films have uniform surfaces with good coverage, as confirmed by SEM images. The inclusion of chlorine and bromine into the structure leads to a lower temperature and shorter reaction time for optimum perovskite film formation. In the case of CH3NH3PbI3?xClx, the optimum reaction temperature is reduced to 100 °C, and the resulting phases are CH3NH3PbI3 (with trace Cl) and CH3NH3PbCl3 with a ratio of about 2:1. In the case of CH3NH3PbI3?xBrx, single‐phase CH3NH3PbI2Br is formed in a considerably shorter reaction time than that of CH3NH3PbI3. The mesostructured perovskite solar cells based on CH3NH3PbI3 films show the best optimal power conversion efficiency of 13.5 %, whereas for CH3NH3PbI3?xClx and CH3NH3PbI3?xBrx the best recorded efficiencies are 11.6 and 10.5 %, respectively.  相似文献   

6.
Syntheses and Structure of Chiral Metallatetrahedron Complexes of the Type [Re2(M1PPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M1 = Ag, Au; M2 = Cu, Ag, Au) From the reaction of Li[Re2(μ‐H)(μ‐PCy2)(CO)7(C(Ph)O)] ( 1 ) with Ph3AuC≡CPh both benzaldehyde and the trinuclear complex Li[Re2(AuPPh3)(μ‐PCy2)(CO)7C≡CPh] ( 2a ) were obtained in high yield. The complex anion was isolated as its PPh4‐salt 2b . The latter reacts with coinage metal complexes PPh3M2Cl [M2 = Cu, Ag, Au] to give chiral heterometallatetrahedranes of the general formula [Re2(AuPPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M2 = Cu 3a , Ag 3b , Au 3c ). The corresponding complex [Re2(AgPPh3)2(μ‐PCy2)(CO)7C≡CPh] ( 3d ) is obtained from the reaction of [Re2(AgPPh3)2(μ‐PCy2)(CO)7Cl] ( 4 ) with LiC≡CPh. 3d undergoes a metathesis reaction in the presence of PPh3CuCl giving [Re2(AgPPh3)(CuPPh3)(μ‐PCy2)(CO)7C≡CPh] ( 3e ) and PPh3AgCl. Analogous metathesis reactions are observed when 3c is reacted with PPh3AgCl or PPh3CuCl giving 3a or 3b , respectively. The reaction of 1 with PPh3AuCl gives benzaldehyde and Li[Re2(AuPPh3)(μ‐PCy2)(CO)7Cl] ( 5a ) which upon reaction with PhLi forms the trinuclear complex Li[Re2(AuPPh3)(μ‐PCy2)(CO)7Ph] ( 6a ). Again this complex was isolated as its PPh4‐salt 6b . In contrast to 2b , 6b reacts with one equivalent of Ph3PAuCl by transmetalation to give Ph3PAuPh and PPh4[Re2(AuPPh3)(μ‐PCy2)(CO)7Cl] ( 5b ). The X‐ray structures of the compounds 3a , 3b , 3e and 4 are reported.  相似文献   

7.
Formation and Reaction of P-functional Phosphanes The reaction of (me3Si)2PLi · 2 THF a (me = CH3) with PCl3 b at ?78°C via the intermediate (me3Si)2P? PCl2 1 yields [(me3Si)2P]2PCl 2 and [(me3Si)2P]2P? P(Sime3)2 3 . By addition of me3CLi c to the reaction mixture of a and b (molar ratio a:b:c (molar ratio a:b:c = 1:1:1) at ?60°C, 2 is formed as a main product, which reacts on to yield [(me3Si)2P]2PH 4 (white crystals, mp = 73°C). By reactions of a:b:c in a molar ratio of 1:1:2 the cyclotetraphosphane (me3C)3 (me3Si)P4 7 is accessible, and the additional formation of (me3Si)2PLi · 2 THF, (me3Si)3P and Li3P7 · 3 THF 13 was detected. Warming (me3Si)2P? PCl(Cme3) 5 to 20°C produces cis- and trans-cyclotetraphosphanes (me3Si)2(me3C)2P4. By running the reaction of a and b at ?78°C and adding me3CLi only after 24 h, additionally to (me3Si)2P? PH Cme3) and (me3Si)3P also (me3Si)2P? P(Cme3)? P(Cme3)? P (Sime3)2 is obtained, which is formed by metallation of (me3Si)2P? PCl(Cme3) with me3CLi and by further reaction of the intermediate (me3Si)2P? PLi(Cme3) with (me3Si)2P? PCl(Cme3). The reaction of (me3Si3)P with PCl3 at ?78°C only yields (me3Si)2P? PCl2 1 and me3SiCl. On addition of me3CLi (?78°C, molar ratio = 1:1:1) preferrably 2 and (me3Si)2P? PCl(Cme3) are formed, whereas after warming the mixture to 20°C, 4 and (me3Si)2P? PH(Cme3) are found to be the main products. These reactions are induced by the cleavage of 1 by means of me3CLi, and by the formation of (me3Si)2PLi and me3C? PCl2.  相似文献   

8.
B3N3Me6Cr(CO)3 reacts with [AsPh4] [SnCl3] and [AsPh4] [GeCl3] in tetrahydrofuran to give [AsPh4]3[Cr(CO)3(SnCl3)3] and [AsPh4]3[Cr(CO)3(GeCl3)3], respectively. According to IR. and 13C-NMR.-data, the tricarbonylate anions possess a meridional configuration. The donor-acceptor properties of SnCl3? and GeCl3? in the anions [Cr(CO)3(ECl3)3]3? (E = Sn, Ge) are very similar. A similar synthesis of [AsPh4]3[Cr(CO)3(SnF3)3] was not successful.  相似文献   

9.
On the Knowledge of the New Ionic Ozonides P(CH3)4O3 and As(CH3)4O3 P(CH3)4O3 and As(CH3)4O3 were prepared via ion exchange in liquid ammonia and characterized by X-ray-powder, IR, MS and DTA techniques. P(CH3)4O3 and As(CH3)4O3 are isotypic and have a wurtzite-like arrangement of ions with rotationally disordered O3?. (Powder data: P63mc; P(CH3)4O3: a = 687.8(2), c = 964.6(3) pm; As(CH3)4O3: a = 708.6(1), c = 991.0(3) pm). As(CH3)4O3 shows a displacive phase transition at ?135°C. The low temperature phase is orthorhombic (a = 715.8(7), b = 1 209(1), c = 943.3(1) pm).  相似文献   

10.
Tetrylidynes [TbbSn≡Co(PMe3)3] ( 1 a ) and [TbbPb≡Co(PMe3)3] ( 2 ) (Tbb=2,6-[CH(SiMe3)2]2-4-(t-Bu)C6H2) are accessed for the first time via a substitution reaction between [Na(OEt2)][Co(PMe3)4] and [Li(thf)2][TbbEBr2] (E=Sn, Pb). Following an alternative procedure the stannylidyne [Ar*Sn≡Co(PMe3)3] ( 1 b ) was synthesized by hydrogen atom abstraction using AIBN from the paramagnetic hydride complex [Ar*SnH=Co(PMe3)3] ( 4 ) (AIBN=azobis(isobutyronitrile)). The stannylidyne 1 a adds two equivalents of water to yield the dihydroxide [TbbSn(OH)2CoH2(PMe3)3] ( 5 ). In reaction of the stannylidyne 1 a with CO2 a product of a redox reaction [TbbSn(CO3)Co(CO)(PMe3)3] ( 6 ) was isolated. Protonation of the tetrylidynes occurs at the cobalt atom to give the metalla-stanna vinyl cation [TbbSn=CoH(PMe3)3][BArF4] ( 7 a ) [ArF=C6H3-3,5-(CF3)2]. The analogous germanium and tin cations [Ar*E=CoH(PMe3)3][BArF4] (E=Ge 9 , Sn 7 b ) (Ar*=C6H3(2,6-Trip)2, Trip=2,4,6-C6H2iPr3) were also obtained by oxidation of the paramagnetic complexes [Ar*EH=Co(PMe3)3] (E=Ge 3 , Sn 4 ), which were synthesized by substitution of a PMe3 ligand of [Co(PMe3)4] by a hydridoylene (Ar*EH) unit.  相似文献   

11.
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12.
Abstract

The reactions of hexachlorocyclotriphosphazatriene, N3 P3 CI6, with 2, 2-dimethylpropane-1, 3-diol yield monospiro-, N3 P3 Cl4 [(OCH2)2 CMe2, dispiro-, N3 P3 Cl4((OCH2)2CMe2|2, and trispiroderivatives, N3 P3 ((OCH2)2, CMe2]3. An ansa, N3 P3 CI4 [(OCH2)2 CMe2]2 and a spiro-ansa, N3 P3 Cl2- ((OCH2), CMe2,]2 and a doubly-bridged compound, (N3 P3 Cl4,)2[(OCH2)]2 were also isolated. Product types and relative yields were compared with those arising from propane-1, 3-diol. The yields of ansa products from the reactions of the dimethyl diol seem to be considerably enhanced relative to those of its unmethylated analogue. 31P and 1H n.m.r. spectra are reported.  相似文献   

13.
Two synthetic routes to 14C-labelled trimethyllead chloride ((CH3)3PbCl) from 14C-methyl iodide (CH3I) were investigated. Alkylation of (CH3)3PbCl with labelled methylmagnesium halide, on a microscale, was less efficient for the synthesis of tetramethyllead ((CH3)4Pb) than was an electrochemical reduction of labelled CH3I at a sacrificial lead cathode. In the Grignard approach, unlabelled decyl bromide served as an initiator for the reaction of 14C-CH3l with excess Mg and as a carrier during the subsequent alkylation of (CH3)3PbCl. In the electrochemical approach a two-compartment cell, using dimethylformamide as solvent and sodium perchlorate as supporting electrolyte, offered several advantages over a single compartment reactor. The labelled (CH3)4Pb from both reactions was isolated by extraction, converted to (CH3)3PbCl by controlled oxidation with HCl and purified by thin layer chromatography.  相似文献   

14.
The reactions of py‐hz ligands ( L1–L5 ) with Pb(CF3SO3)2?H2O resulted in some rare examples of discrete single‐stranded helical PbII complexes. L1 and L2 formed non‐helical mononuclear complexes [Pb L1 (CF3SO3)2]?CHCl3 and Pb L2 (CF3SO3)2][Pb L2 CF3SO3]CF3SO3?CH3CN, which reflected the high coordination number and effective saturation of PbII by the ligands. The reaction of L3 with PbII resulted in a dinuclear meso‐helicate [Pb2 L3 (CF3SO3)2Br]CF3SO3?CH3CN with a stereochemically‐active lone pair on PbII. L4 directed single‐stranded helicates with PbII, including [Pb2 L4 (CF3SO3)3]CF3SO3?CH3CN and [Pb2 L4 CF3SO3(CH3OH)2](CF3SO3)3?2 CH3OH?2 H2O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with PbII, including a trinuclear PbII complex [Pb3 L5 (CF3SO3)5]CF3SO3?3CH3CN?Et2O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with PbII.  相似文献   

15.
The reaction of (CH3)2AsJ and AgN3 yields (CH3)2AsN3; a colourless liquid (b. p. 136°C) which dissolves as a monomeric in benzene. (CH3)2BiN3 is precipitated in form of colourless needles (dec. temp. 150°C) from an etherical solution of Bi(CH3)3 and HN3. According to its vibrational and mass spectra the molecules are not associated although the (CH3)2BiN3 is not soluble; dipole association of this polar molecules is assumed for the crystal structure. (CH3)2TlN3 can be obtained from TI(CH3)3 and ClN3 as well as from (CH3)2TlOH and HN3 in form of colourless needles and leaves (dec. temp. 245°C). According to its vibrational spectra it has an ionic structure, (CH3? Tl? CH3)+N?3.  相似文献   

16.
CF3SO2N?SCl2 reagiert mit (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 oder (C5H10)S[NSi(CH3)3]2 unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S4N4-Derivaten S4N4(NSO2CF3)2(CH3)4 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna21 mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, dx = 1,815 g cm?3 und Z = 4. Die mittleren S? N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å. CF3SO2N? SCl2 reagiert mit trimethylzinnhaltigen S? N-Verbindungen zum bekannten CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 und Dimethylzinndichlorid. Synthesis and X-Ray Structure Analysis of S4N4-Derivatives with Threefold and Fourfold Coordinated Sulfur Atoms CF3SO2N?SCl2 reacts with (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 or (C5H10S[NSi(CH3)2]2 under elimination of (CH3)3SiCl to yield the eight-membered S4N4 derivatives S4N4?NSO2CF3)2(CH3)4, 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna21 with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, dx = 1.815 g cm?3, and Z = 4. The average S? N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF3SO2N=SCl2 reacts with trimethyl tin-containing S? N compounds to the known CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 and dimethyl tin dichloride.  相似文献   

17.
Rubidium metaborate, Rb3B3O6, was obtained by the reaction of Rb2CO3 and BN using a radiofrequency furnace at a maximum reaction temperature of 1173 K. The crystal structure has been determined by single‐crystal X‐ray diffraction. The space group is , with all atoms positioned on a twofold axis (Wyckoff site 18e). The ionic compound is isotypic with Na3B3O6, K3B3O6 and Cs3B3O6.  相似文献   

18.
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   

19.
The novel copper iodide clusters [Cu3(μ‐I)(μ3‐I)2(PH2BH2·NMe3)3] ( 2 ) and [Cu4(μ‐I)2(μ3‐I)2(PH2BH2·NMe3)3] ( 3 ) were synthesized by treating CuI with the primary phosphine (H2PBH2·NMe3). The novel features of both compounds, which have been characterized by X‐ray crystallography, are the unsymmetrical constitution of the copper iodide core due to the influence of the monodentate phosphorus ligand. This results in copper atoms with different coordination numbers within the compound. Complex 2 , the major product of the reaction, contains a distorted octahedral Cu3I3‐core, in which one vertex is missing. Complex 3 was isolated as a by‐product and is composed of a Cu4I4‐core in a distorted octahedral coordination.  相似文献   

20.
Zusammenfassung Mo3CoB3, Mo3NiB3, W3CoB3 und W3NiB3 kristallisieren in einem eigenen Typ (W3CoB3-Struktur). Das trigonal prismatische Bauelement [T 6B]* ist zu Ketten vereinigt, wobei B3-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.
The crystal structure of W3CoB3 and the isotypic phases Mo3CoB3, Mo3NiB3, and W3NiB3
Mo3CoB3, Mo3NiB3, W3CoB3, and W3NiB3 were found to possess a new type of crystal structure (W3CoB3-structure type). Trigonal prismatic groups [T 6B]* are linked together forming chains in such a way that B3-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

Mit 2 Abbildungen  相似文献   

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