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31.
Joseph Grobe Duc Le Van Franz Immel Marianne Hegemann Bernt Krebs Mechtild Lge 《无机化学与普通化学杂志》1996,622(1):24-34
Reactive E = C(pp)π-Systems. XLII [1]. Novel Coordination Compounds of 2-(Diisopropylamino)-1-phosphaethyne: [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}], [(Ph3P)2Pt{η2-(iPr2NCP)}], and [Co2(CO)6{η2-μ2-(iPr2NCP)}] 2-(Diisopropylamino)-phosphaethyne iPr2N? C?P ( 2 ) reacts with the Ni(0)-complexes [Ni(1,5-cyclooctadiene)2] and [Ni(CO)3(1-azabicyclo[2.2.2]octane)], respectively, to give the novel complex [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}] ( 5 ), with the 1,3-diphosphacyclobutadiene derivative and 2 (side-on) as π-ligands. The molecular structure of 5 determined by X-ray diffraction on single crystals proves the spin systems and rotational barriers deduced from NMR-data (1H, 13C-, 31P). The PC distances of the four-membered ring of 1.817(2) and 1.818(2) Å – as expected – are considerably longer than the PC bond of the η2-coordinated phosphaalkyne 2 [1.671(2) Å]. – In the reactions of 2 with [(Ph3P)2Pt(C2H4)] or [Co2(CO)8] the ligand properties of 2 resemble those of alkynes affording the complexes [(Ph3P)2Pt{η2-(iPr2NCP)}] ( 7 ) with side-on coordinated 2 and [Co2(CO)6{η2-μ2-(iPr2NCP)}] with 2 acting as a 4e donor bridge in quantitative yield. In attempts to prepare copper(I) complexes of the aminophosphaalkyne 2 by reaction with CuCl or CuI the only isolable product formed in reasonable amounts under the influence of air and moisture is the 1 λ3, 3 λ5-diphosphetene (iPr2N) ( 10 ) (isolated yield: ca. 20%). The crystal structure analysis of 10 indicates a strong structural relationship to the diamino-2-phosphaallyl cation [Me(iPr2N)]+ ( 12 ), the 1,3-diphosphacyclobutadiene ligand (iPr2NCP)2 in the binuclear complex [{η1, μ2-(iPr2NCP)2}Ni2(CO)6] ( 3a ) as well as to the heterocycles (dme)2LiOE2′ (E′ = S, 11a ; E′ = Se, 11b ) prepared by Becker et al. [11b, 35]. 相似文献
32.
Sarah Fakih Wing Chau Tung Dirk Eierhoff Christian Mock Bernt Krebs 《无机化学与普通化学杂志》2005,631(8):1397-1402
In modern cancer therapy the clinical application of platinum‐based drugs is more and more limited by the occurrence of intrinsic or acquired resistances. In this context the potential use of dinuclear platinum complexes in chemotherapy is increasingly relevant. The novel complexes Pd(Bzdpa)Cl2, Pd2(C4H8(dpa)2)Cl4, and Pt2(C4H8(dpa)2)Cl4 allow a direct comparison of mono‐ and dinuclear palladium and platinum complexes respectively deriving from a 2,2′‐dipyridylamine (Hdpa) ligand system. They were characterized by single crystal X‐ray analysis as well as infrared spectroscopy and elemental analysis. The cisplatin analogous mononuclear palladium complex Pd(Bzdpa)Cl2 ( 1 ) (Bzdpa: (2,2′‐dipyridylbenzyl)amine) belongs to a range of 2,2′‐dipyridylamine‐based compounds which were extensively studied in our laboratories. 1 crystallizes in the orthorhombic space group Pna21 with a = 13.722(3), b = 13.457(3), c = 9.483(2), V = 1751.1(6) Å3, and Z = 4. The metal binding motif of 1 was expanded by a flexible butyl‐linker to form the tetradentate C4H8(dpa)2 ligand. The resulting isotypic dinuclear complexes Pd2(C4H8(dpa)2)Cl4·2CH3CN ( 2 ) and Pt2(C4H8(dpa)2)Cl4·2CH3CN ( 3 ) crystallize in the triclinic space group with a = 7.8427(2), b = 8.7940(2), c = 11.7645 (3), α = 79.219(2)°, β = 84.033(2)°, γ = 87.744(2)°, V = 792.58(3) Å3 ( 2 ) and a = 7.831(5), b = 8.814(5), c = 11.817(5), α = 79.271(5)°, β = 83.571(5)°, γ = 88.063(5)°, V = 796.3(8) Å3 ( 3 ), both with one centrosymmetrical molecule in the unit cell. 相似文献
33.
Alternative Ligands. XXXII [1]. Novel Tetraphosphane Nickel Complexes with Tripod-Ligands of the Type XM′(OCH2PMe2)n(CH2CH2PR2)3 – n (M′ = Si, Ge; n = 0 – 3) Tripod Ligands of the type XM′(OCH2PMe2)n(CH2CH2PMe23 – n (M′ = Si, Ge; n = 0 – 3) ( 1 – 6 , Table 1) have been used together with PPh3 or PMe3 for the preparation of novel tetraphosphane complexes of Nickel. The representatives LNiPPh3 ( 7 – 12 ) are obtained by reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with the corresponding ligands and PPh3 in toluene in moderate yields. The synthesis of the derivatives LNiPMe3 ( 13 – 18 ) is partly ( 16 – 18 ) accomplished in analogy to the Ph3P-complexes; compounds 13 – 16 are obtained in higher yields by reaction of Ni(PMe3)4 with the respective ligand. As a rule, 13 – 18 cannot be separated from by-products. The trinuclear complex FSi(CH2CH2PMe2)3[Ni(PMe2CH2CH2)3SiF]3 ( 19 ) is formed together with 18 in the reaction of Ni(COD)2 with 6 and PMe3. The new compounds have been characterized (if possible) by analytical (C, H), but in general by spectroscopic investigations (IR; 1H-, 13C-, 19F-, 31P-NMR; MS). A weak, but significant Ni → Si interaction through the cage is indicated by the following results: (i) Large low-field shifts δδF of 35.2 ppm ( 12 ), 38.3 ppm ( 18 ) and 37.7 ppm ( 19 ); (ii) 6J(PF) coupling constants [or 3J(PNiSiF) through the cage] of 6.0 Hz ( 12 ) and 7.6 Hz ( 18 ) together with a low-field shift δδSi of 12.8 ppm ( 12 ); (iii) NiSi distances of 3.95 Å in 7 and 3.92 Å in 12 , accompanied by a compression of the cage along the Ni ··· Si axis. An additional release from the high charge density on Ni results from π-backbonding to the phosphane ligands. 相似文献
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38.
New Oxonium Bromochalcogenates(IV) — Synthesis, Structure, and Properties of [H3O][TeBr5] · 3 C4H8O2 and [H3O]2[SeBr6] Dark red crystals of the composition [H3O][TeBr5] · 3 C4H8O2 ( 1 ) were isolated from a saturated solution of TeBr4 in 1,4-dioxane containing a small amount of water. In this compound (space group P21/m, a = 8.922(4) Å, b = 13.204(7) Å, c = 9.853(5) Å, β = 91.82(4)° at 150 K) a square pyramidal [TeBr5]? anion has been isolated for the first time. The coordination sphere of the anion is completed to a distorted octahedron by weak interaction with a dioxane molecule of the cationic system. The [H3O]+ cations are connected to chains by dioxane molecules. At room temperature the compound is stable only in its mother liquor. Crystalline [H3O]2[SeBr6] ( 2 ) (space group Fm3m, a = 10.421(1) Å at 170 K) is a bromoselenous acid of high symmetry. The [H3O]+ ion is only weakly coordinated by Br atoms of the anion. The anions are isolated octahedral [SeBr6]2? units. The structure is isotypic to the K2[PtCl6] structure. Despite being a halogenochalcogen(IV) acid, 2 exhibits a remarkable thermal stability. Both oxonium compounds were characterized by single-crystal X-ray structure analyses. Vibrational spectra of 2 are reported. 相似文献
39.
A series of novel lanthanide polyoxometalates: condensation of building blocks dependent on the nature of rare earth cations 总被引:1,自引:0,他引:1
A series of novel lanthanide polyoxomolybdates was synthesized by reaction of lanthanide cations with the Anderson type anion (TeMo(6)O(24))(6-). The polyoxometalates K(6n)(TeMo(6)O(24))(n)[(Ln(H(2)O)(7))(2)(TeMo(6)O(24))](n)[middle dot]16nH(2)O (Ln = Eu, Gd) and K(3n)[Ln(H(2)O)(5)(TeMo(6)O(24))](n)[middle dot]6nH(2)O (Ln = Tb, Dy, Ho, Er) were characterized by X-ray structure analysis, elemental analysis and IR spectroscopy. We found that the solid-state structures of Ln/(TeMo(6)O(24))(6-) compounds are strongly dependent on the lanthanide cations, and therefore represent a rare example for different arrangements of building units depending on the nature of the rare earth cations. While the Eu(3+) and Gd(3+) cations achieve ninefold coordination by seven water molecules and two terminal oxygen atoms of the (TeMo(6)O(24))(6-) anions, the Tb(3+), Dy(3+), Ho(3+) and Er(3+) cations are coordinated by five water molecules, two terminal oxygen atoms and one molybdenum-bridging oxygen atom belonging to the (TeMo(6)O(24))(6-) anion. The europium and gadolinium substituted compounds contain infinite one-dimensional [(Ln(H(2)O)(7))(2)(TeMo(6)O(24))](n) chains; the terbium, dysprosium, holmium and erbium compounds contain infinite one-dimensional [Ln(H(2)O)(5)(TeMo(6)O(24))](n)(3n-) chains. 相似文献
40.
Petra Schulte Gunther Schmidt Claus-Peter Kramer Adolf Krebs Ulrich Behrens 《Journal of organometallic chemistry》1997,530(1-2):95-100
The strained cycloheptynes 2a, 2b and 2c react with copper(I) chloride to form the dinuclear complexes [CuCl(cycloheptyne)]2 3a, 3b and 3c respectively. X-ray diffraction studies on all three compounds 3 show an increase in strength of the copper-alkyne bond with increasing deformation of the alkyne moiety from the ideal 180°. Thus going from the least strained alkyne (2c) to the most strained one (2a), the Cu-C bond lengths in the corresponding complexes decrease from 197.5 pm (3c) to 194.9 pm (3a). The C≡C-C angles increase from 145.6° (3a) over 147.4° (3b) to 151.6° (3c).
Zusammenfassung
Die gespannten Cycloheptine 2a, 2b und 2c reagieren mit Kupfer(I)—chlorid unter Bildung der zweikernigen Komplexe [CuCl(cycloheptin)]2 3a, 3b und 3c. Röntgenstrukturanalysen von allen drei Verbindungen 3 zeigen, daβ die Stärke der Kupfer—Alkin-Bindung zunimmt je mehr das ganze Alkinsystem vom idealen 180°-Winkel abweicht. Geht man vom am wenigsten gespannten Alkin (2c) zum gespanntesten (2a), so nehmen die Cu-C-Bindungslängen in den entsprechenden Komplexen von 197.5 pm (3c) auf 194.9 pm (3a) ab. Die C≡C-C-Winkel werden von 145.6° (3a) über 147.4° (3b) nach 151.6° (3c) hin gröβer. 相似文献