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1.
[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   

2.
Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. IV. Formation and Structure of the Chromium Carbonyl Complexes of Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu2P)3P7 The reaction of (t-Bu2P)3P7 1 with Cr(CO)5 · THF in a molar ratio of 1:1 yields yellow crystals of (t-Bu2P)3P7[Cr(CO)5] 2 having the Cr(CO)5 group coordinated to a Pb atom (basal) of the three membered ring. With a molar ratio of 1:2 compounds 2 , (t-Bu2P)3P7[Cr(CO)5]2 3 , (t-Bu2P)3P7[Cr(CO)5][Cr(CO)4] 4 and (t-Bu2P)3P7[Cr(CO)4]2 5 were obtained. In 3 (yellow crystals) one Cr(CO)5 group is linked to a Pb atom, the other one to an exocyclic Pexo atom. On irradiation 3 loosing one CO group generates 4 (orange red crystals) with an unchanged Cr(CO)5 group linked to the Pb atom and a five membered chelate-like ring containing an apical Pa atom, two equatorial Pa atoms, one Pexo atom and the Cr atom of the carbonyl group. Compound 5 (orange red crystals) contains two such five membered rings. (t-Bu2P)3P7[Cr(CO)4]3 6 (red needles) is formed with Cr(CO)5 · THF in a molar ratio of 1 : 1. However, even with higher amounts of Cr(CO)5 · THF and after extended reaction times, only 6 is formed; no further Cr carbonyl group could be attached to the P skeleton. With Cr(CO)5 · NBD in a molar ratio of 1 : 1, (t-Bu2P)3P7[Cr(CO)4] 7 is produced from 1, and 5 with a molar ratio of 2 : 1. As in 4, the Cr(CO)4 group in 7 (orange crystals) participates in a five membered chelate-like ring. It was not possible to generate 6 from 5 with an excess of Cr(CO)4 · NBD and with extended reaction times. The molecular structures of the compounds were identified by investigating the 31P[1H] NMR spec-tra and considering especially the coordination shift, and by crystal structure determinations of 2 and 4. Compound 2 crystallizes in the space group PI (no.2) with a = 1566.2(4) pm, b = 2304.1(5) pm, c = 1563.3(4) pm,α = 95.57(3)°, β = 108.79(3)°, γ = 109.82(4)° and Z = 4 formula units in the elementary cell. Compound 4 crystallizes in the space group P 21 /n (no. 14) with a = 1416.6(5) pm, b = 2573.6(5) pm, c = 1352.9(4) pm,β = 99.17(5)° and Z = 4 formula units in the elementary cell.  相似文献   

3.
Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII. Formation and Structure of [Li(DME)3]2{(SiMe3)[Cr(CO)5]2 P-P ? P-P[Cr(CO)5]2(SiMe3)} Deep red crystals of the title compound 1 are produced in the reaction of LiP(Me3Si)2[Cr(CO)5] with 1, 2-dibromoethane in DME. The structure of 1 was derived from the investigation of the 31P-NMR spectra and confirmed by a single crystal structure determination. 1 crystallizes in the space group P1 (no. 2); a = 1307.8(5)pm, b = 1373.1(5)pm, c = 1236.1(4)pm, α = 106.22(4)°, β = 88.00(3)°, γ = 115.52(4)° and Z = 1. 1 forms a salt composed of a dianion R2R4′P42? (R ? SiMe3, R′ ? Cr(CO)5) and solvated Li+ cations. The zigzag shaped dianion possesses the symmetry 1 -Ci. The distances d(P? P) = 202.5(1)pm and d(P? P) = 221.9(1)pm correspond to a double bond and single bonds, respectively. The distances d(Cr? P) = 251.1(1) pm and 255.3(1) pm are larger than those observed so far which might be caused by the charge distribution in the dianion.  相似文献   

4.
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   

5.
New Research of Reaction Behaviour of Triorganylcyclotriphosphines. The Crystal Structures of [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)62-CO)3{(PtBu)2}2], and [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)] By the reaction of triorganylcyclotriphosphines with transition metal complexes single- and polynuclear compounds are formed, in which the cyclophosphines are bonded in different ways to the metal, the ring either preserving structure or under going ring opening. Depending on the reaction conditions the following compounds can be characterized: [(PPh3)2Pt(PtBu)3] ( 1 ), [(PPh3)2Pd(PtBu)2] ( 2 ), [(CO)4Cr{(PiPr)3}2] ( 3 ), [RhCl(PPh3)(PtBu)3] ( 4 ), [(NiCO)62-CO)3{(PtBu)2}2] ( 5 ) and [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)] ( 6 ). The structures of 1 – 6 were obtained by X-ray single crystal structure analysis ( 1 : space group P21/n (No. 14), Z = 4, a = 1279.6(3) pm, b = 1733.1(4) pm, c = 2079.1(4) pm, β = 90.20(3)°; 2 : space group P21/c (No. 14), Z = 4, a = 1053.3(2) pm, b = 2085.2(4) pm, c = 1855.7(4) pm, β = 98.77(3)°; 3 : space group P 1 (No. 2), Z = 2, a = 1022.6(2) pm, b = 1026.4(2) pm, c = 1706.0(3) pm, α = 82.36(3)°, β = 86.10(3)°, γ = 64.40(3)°; 4 : space group P 1 (No. 2), Z = 2, a = 980.2(2) pm, b = 1309.5(3) pm, c = 1573.4(3) pm, α = 99.09(3)°, β = 99.46(3)°, γ= 111.87(3)°; 5 : space group P21/c (No. 14), Z = 4, a = 1804.0(5) pm, b = 2261.2(6) pm, c = 1830.1(7) pm, β = 96.99(3)°; 6 : space group P21/c (No. 14), Z = 4, a = 943.2(3) pm, b = 2510.6(7) pm, c = 1325.1(6) pm, β = 98.21(3)°).  相似文献   

6.
Tris[3‐hydroxy‐2(1 H)‐pyridinonato] Complexes of Al3+, Cr3+, and Fe3+ – Crystal and Molecular Structures of 3‐Hydroxy‐2(1 H)‐pyridinone and Tris[3‐hydroxy‐2(1 H)‐pyridinonato]chromium(III) Tris[3‐hydroxy‐2(1 H)‐pyridinonato] complexes of Al3+, Cr3+ and Fe3+ are obtained by reactions of 3‐hydroxy‐2(1 H)pyridinone with the hydrates of AlCl3, CrCl3 or Fe(NO3) in aqueous alkaline solutions as polycrystalline precipitates. The compounds are isotypic. X‐ray structure determinations were performed on single crystals of the uncoordinated 3‐hydroxy‐2(1 H)‐pyridinone ( 1 ) (orthorhombic, space group P212121, a = 405.4(1), b = 683.0(1), c = 1770.3(3) pm, Z = 4) and of the chromium compound 3 (rhombohedral with hexagonal setting, space group R3c, a = 978.1(1), c = 2954.0(1) pm, Z = 6).  相似文献   

7.
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   

8.
Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu2P? P?P(Me)tBu2 1, tBu(Me3Si)P? P?P(Me)tBu2 2, and tBu2P? P?P(Br)tBu2 3 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me2SO4 or CH3Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P21/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R2P? P(?)? P(+)(X)R2. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R2P? P(X)? PR2.  相似文献   

9.
New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)· (PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2], and [Ni8(PtBu)6(PPh3)2] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co4(CO)10 · (PiPr)2] ( 2 ), [Fe3(CO)9(PtBu)(PPh)] ( 3 ), [Cp3Fe3(CO)2(PPtBu) · (PtBu)] ( 4 ), [(NiPPh3)2(PiPr)6] ( 5 ), [(NiPPh3)Ni{(PtBu)3}2] ( 6 ) and [Ni8(PtBu)6(PPh3)2] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P21 (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).  相似文献   

10.
New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6], and [Ni4(CO)10(PiPr)6], (PtBu)3 reacts with [Mn2(CO)10], [Re2(CO)10], [Co2(CO)8] and [Ir4(CO)12] to form the multinuclear complexes [M2(CO)7(PtBu)3] (M = Re ( 1 ), Mn ( 5 )), [Co4(CO)10(PtBu)2] ( 2 ) and [Ir4(CO)6(PtBu)6] ( 3 ). The reaction of (PiPr)3 with [Ni(CO)4] leads to the tetranuclear cluster [Ni4(CO)10(PiPr)6] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P21/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).  相似文献   

11.
Structural Chemistry of Phosphorus Containing Chains and Rings. 16. Molecular and Crystal Structure of the Triisopropylundecaphosphane P11(i-Pr)3 The compound 4,7,11-triisopropyl-pentacyclo[6.3.0.02.6.03.10.05.9]undecaphosphane, C9H21P11, crystallizes triclinically in the space group P1 with a = 1 045.3 pm, b = 1 057.2 pm, c = 1 075,0 pm, α = 101.00°, β = 98.89°, γ = 112.27° and Z = 2. The main structural feature is a phosphorus skeleton with approximate symmetry D3 composed of six five-membered rings which are asymmetrically substituted by the isopropyl groups. The (average) bond lengths are d(P? P) = 221.6 pm, d(P? C) = 187.5 pm, d(C? C) = 151.4 pm, d(C? H) = 108 pm with 217.6 ≤ d(P? P) ≤ 226.4 pm. The geometry of the substituents is quite normal.  相似文献   

12.
Mono- and Di-t-Butylcyclopentadienyl Carbonyl Complexes of Iron and Molybdenum — Crystal Structure of [Cp″Mo(CO)2]2 (Cp″ = n5-C5H3-t-Bu2-1,3) Cothermolysis of M(CO)m (M = Fe, m = 5; M = Mo, m = 6) with t-Bu-substituted cyclopentadienyls constitutes a simple synthesis of complexes of the type [Cp*M(CO)n]2 (CP* = n5-C5H3 (t-Bu), R, R = H, t-Bu; M = Fe, Mo; n = 2, 3). Each synthesis has an optimal temperature. The yield of Fe complexes decreases at temperatures above 130°C because of decomposition of the product. Optimal yields of [Cp*Mo(CO)3]2 are obtained at 130–140°C, whereas at 160°C complexes of the type [Cp*Mo(CO)2]2 with formal Mo? Mo triple bonds are obtained. The structure of the complexes is discussed on the basis of 1H-, 13C-NMR, IR, and mass spectrometry. The structure of [Cp″Mo(CO)2]2 (Cp″ = n5-C5H3t-Bu2-1,3) was determined by X-ray crystallography at ?95°C. It crystallises in the space group Pbca, with cell constants a = 1808.6(6), b = 1308.5(4), c = 2507.9(9) pm, Z = 8, R = 0.031 for 3794 reflections. The Mo? Mo bond length of 253.3 pm is very long for a formal triple bond. The Cp″? Mo? Mo? Cp″ axis is non-linear.  相似文献   

13.
Cluster Synthesis by Photolysis of R3PAuN3. VIII. Synthesis and Crystal Structure of [(Ph3PAu)5Mo(CO)4]PF6 · CH2Cl2 and (Ph3PAu)3Co(CO)3 Photolysis of a mixture of Ph2PAuN3 and Mo(CO)6 in THF yields [(Ph3PAu)5Mo(CO)4]+ (1), which can be crystallized from CH2Cl2/diisopropylether as orange 1 · PF6 · CH2Cl2 with the space group P21/c and a = 1681.4(5), b = 2215.6(12), c = 2761.5(9) pm, β = 91.54(3)°, Z = 4. The Au5Mo center of cluster 1 forms a capped trigonal bipyramid with the Mo atom in equatorial position and almost equal Mo? Au distances between 279.9(5) and 284.6(7) pm to all five Au atoms. The Au? Au distances range from 272.2(4) to 301.3(4) pm. The Mo(CO)4 group causes three v(C0) at 1975, 1915 and 1890cm?1. Reaction of Ph3PAuCo(CO)4 with Ph3PAuPF6 affords the known cluster cation [(Ph3PAu)4Co(CO)3]+ in high yield. It can be degraded with C1? to the neutral cluster (Ph3PAu)3Co(CO)3 (2). 2 forms air stable, yellow crystals with the space group P21/n and a = 1359.4(4), b = 2041.0(5), c = 1853.2(6)pm, β = 91.47(1)°, Z = 4. The Au3Co core of 2 has a tetrahedral structure with distances Co? Au between 250.4(1) and 254.0(2) pm and Au? Au between 279.5(1) and 285.1(1) pm. v(C0) are observed at 1963, 1905 and 1891 cm?1. Reaction of 2 with [(Ph3PAu)4Co(CO)3]+ yields the condensed cluster [(Ph3PAu)6AuCo2(CO)6]+.  相似文献   

14.
Crystal and Molecular Structure of fac-Trichloro-tris(dimethyl sulfoxide)bismuth(III) BiCl3(DMSO)3 Crystals of the known, although structurally not characterized title compound were fortuitously obtained from a reaction mixture containing (CH3)3SiN(SO2CH3)2, BiCl3, DMSO, CH2Cl2 and CH3NO2. Crystallographic data (at ?130°C): triclinic, space group P1 1, a = 816.1(5), b = 885.1(6), c = 1 360.6(8) pm, α = 77.58(3), β = 77.39(3), γ = 64.42(3)°, U = 0.8569 nm3, Z = 2. The DMSO ligands are bound through oxygen to the Bi atom. Important bond distances and angles in the resulting fac-octahedral complex are as follows: Bi? Cl 258.9, 261.0, 263.0, Bi? O 242.6, 245.7, 246.1 pm; Cl? Bi? O (trans) 170.3, 170.6, 176.9, Cl? Bi? Cl 94.6, 94.7, 96.0, O? Bi? O 81.7, 85.4, 87.9, Cl? Bi? O (cis) in the range 87.2–92.6, Bi? O? S 123.4, 126.1, 129.6°.  相似文献   

15.
Synthesis and Characterization of [Zn{Si(NMe2)2(NHCMe3)(NCMe3)}(μ‐NC5H4)]2, a Molecular Single Source Precursor for ZnSiN2 For an application as single source precursor for ZnSiN2 the siladiazazinca cyclo butane [Zn{Si(NMe2)2(NHCMe3)(NCMe3)}(μ‐NC5H4)]2has been synthesised for the first time from Si(NMe2)2(NLi t‐Butyl)2 and ZnCl2(NC5H5)2. It has been characterized by single crystal structure analysis (P1, a = 870.5(3) pm, b = 903.8(3) pm, c = 1530.6(4) pm, α = 96.982(5)°, β = 106.501(5)°, γ = 104.729(5)°). The CP‐MAS‐NMR data for the nuclei 13C, 15N and 29Si are reported. ZnSiN2 was prepared by thermal decomposition of the precursor molecule and characterized by elemental analysis, EDX, IR spectroscopy and thermal analysis. The crystal structure was determined (X‐ray powder diffraction data, profile matching: P63mc, a = 315.33(1) pm, c = 508.07(2) pm, RB = 4.87). The thermal behaviour of the precursor molecule, the preparation of polymers by linking with NH3 and the decomposition of the polymers in an argon or NH3 stream were investigated.  相似文献   

16.
Cluster Synthesis by Photolysis of Azido Complexes of Platinum and Gold. Syntheses and Crystal Structures of [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] and [(Ph3PAu)4Pt(dppe)](PF6)2 Photolysis of a mixture of Ph3PAuN3, Ph3PAuCl and (Ph3P)2Pt(N3)2 in THF yields after chromatographic separation with CH2Cl2/EtOH as eluens the cluster [(Ph3PAu)6(AuCl)3Pt(CO)] ( 1 ). It crystallizes in the triclinic space group P1 with the lattice parameters a = 2 139.3(4), b = 2 457.1(4), c = 2 561.9(1) pm, α = 79.74(9)°, β = 80.06(6)°, γ = 66.05(5)°, Z = 4. The nine gold atoms form a fragment of an icosahedron with the platinum atom in its center. Upon photolysis of (dppe)Pt(N3)2 with Co2(CO)8 in THF one m?2-CO ligand of the cobalt carbonyl is substituted by a (dppe)Pt group. The resulting cluster [(dppe)PtCo2(CO)7] ( 2 ) crystallizes monoclinically in the space group P21/n with a = 1 303.9(3), b = 1 768.1(8), c = 1 461.4(4) pm, β = 102.81(1)°, Z = 4. Photolysis of 2 with excess Ph3PAuN3 affords the clusters [(Ph3PAu)4Pt(dppe)]2+ ( 3 ), and [(Ph3PAu)6AuCo2(CO)6]+. 3 crystallizes with PF as counterions in the triclinic space group P1 with a = 1 369.1(4), b = 1 505.0(4), c = 2 773.0(8) pm, α = 84.74(1)°, β = 87.37(2)°, γ = 65.94(2)°, Z = 2. The Au4Pt skeleton of 3 forms a trigonal bipyramid with the platinum atom in equatorial position.  相似文献   

17.
Structural Chemistry of Phosphorus Containing Chains and Rings. 7. Molecular and Crystal Structure of the Diphosphagermetane (t-BuP)2(GePh2)2 The compound 1,2-di-tert-butyl-3,3,4,4-tetraphenyl-diphospha-3,4-digerma-cyclobutan, (t-BuP)2(GePh2)2, crystallizes monoclinically in the space group P21/c with a = 996.8 pm, b = 1337.3 pm, c = 2403.4 pm, β = 92.66° and Z = 4 formula units. The main structural feature is a non-planar four-membered ring. The (average) bond lengths are d(Ge? Ge) = 242.1 pm, d(Ge? P) = 234.0 pm, d(P? P) = 221.6 pm, d(Ge? C) = 194.9 pm, d(P? C) = 188.tyl4 pm, d(C? C)Ph = 136.l5 pm, d(C? C)t-Bu = 151.8 pm, d(C? H)Ph = 91 pm, d(C? H)t-Bu ? 95 pm. The geometry of the substituents phenyl and tert-butyl is quite normal.  相似文献   

18.
Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe2(CO)6(PR)6] (R = tBu, iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6], and [Ir4(C8H12)4Cl2(PPh)4] (PtBu)3 and (PiPr)3 react with [Fe2(CO)9] to form the dinuclear complexes [Fe2(CO)6(PR)6] (R = tBu: 1 ; iPr: 2 ). 2 is also formed besides [Fe2(CO)4(PiPr)6] ( 3 ) in the reaction of [Fe(CO)5] with (PiPr)3. When PiPr(PtBu)2 and PiPrCl2 are allowed to react with [Fe2(CO)9] it is possible to isolate [Fe2(CO)3Cl2(PtBu)5] ( 4 ). The reactions of (PiPr)3 with [Co2(CO)8] and [Ni(CO)4] lead to the tetra- and pentanuclear clusters [Co4(CO)10(PiPr)3] ( 5 ), [Ni4(CO)10(PiPr)6] [2] and [Ni5(CO)10(PiPr)6] ( 6 ). Finally the reaction of [Ir(C8H12)Cl]2 with K2(PPh)4 leads to the complex [Ir4(C8H12)4Cl2(PPh)4] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P21/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P21/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P21/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).  相似文献   

19.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co4P2(PtBu2)2(CO)8] and [{Co(CO)3}2P4tBu4] from Co2(CO)8 and tBu2P–P=P(Me)tBu2 Co2(CO)8 reacts with tBu2P–P=P(Me)tBu2 yielding the compounds [Co4P2(PtBu2)2(CO)8] ( 1 ) and [{η2tBu2P=P–P=PtBu2}{Co(CO)3}2] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ2‐bridged by tBu2P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)3 units is η2‐coordinated to the terminal P2 units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P21/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.  相似文献   

20.
Cs[Er10(C2)2]I18 and [Er10(C2)2]Br18: Two New Examples for Reduced Halides of the Lanthanides with Isolated [M10(C2)2] Clusters Cs[Er10(C2)2]I18 is obtained from the reaction of ErI3 with caesium and carbon in sealed tantalum containers at 700°C and [Er10(C2)2]Br18 through the metallothermic reduction of ErBr3 with rubidium in the presence of carbon at 750°C in sealed niobium containers. The crystal structures {Cs[Er10(C2)2]I18: triclinic, P1 ; a = 1 105.2(8) pm, b = 1 112.0(7) pm; c = 1 122.9(8) pm; α = 66.91(3)°, β = 87.14(3)°; γ = 60.80(3)°; Z = 1; R = 0.049, Rw = 0.043; [Er10(C2)2]Br18: monoclinic, P21/n, a = 971.8(6) pm, b = 1 623.4(9) pm, c = 1 163.8(6) pm, β = 104.00(6)°; Z = 2; R = 0.077, Rw = 0.057} contain isolated dimeric [Er10(C2)2] clusters. Due to the inclusion of C2 units, the octahedra are elongated in the direction of the pseudo C4 axis. The connecting edges of the two octahedra are exceptionally short (316.7 pm and 314.8 pm respectively). The dimeric units are connected via Xi?a and Xa?i (X = Br, I) bridges according to [Er10(C2)2XX]X. Cs+ is surrounded by a cuboctahedron of iodide ions in Cs[Er10(C2)2]I18.  相似文献   

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