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Intramolecular Antiferromagnetism in [Cr2(μ-NH2)3(NH3)6]I3 The magnetism of [Cr2(μ-NH2)3(NH3)6]I3 which consists of binuclear cations with NH2?-bridged face-sharing octahedral coordination polyhedra and a metal-metal separation of 264.9 pm can be explained by antiferromagnetically exchange-coupled CrIII-3d3 pairs. The magnetochemical analysis in the temperature range 5 K – 295 K on the basis of the isotropic Heisenberg model (spin Hamiltonian ? = ?2 J?1 · ?2) leads to the parameter value J = ?98(3) cm?1. Compared to the exchange coupling in corresponding binuclear chromium compounds with OH? bridges and identical metal-metal separation the strength of the coupling is significantly enhanced (JNH2/JOH ≈? 1.6).  相似文献   

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The compounds [Hg2(μ—SePh)2(SePh)2(PPh3)2] ( I ) and [Hg3Br3(μ—SePh)3] · 2 DMSO ( II ) are formed by reactions of [Hg(SePh)2] with PPh3 in THF( I ) or with HgBr2 in DMSO ( II ) at room temperature. X—ray crystallography reveals that the cluster I consists of a distorted square built by each two Hg and Se atoms. The Hg atoms have almost tetrahedral co‐ordination environments formed by selenium atoms of two (μ‐SePh) ligands and Se and P atoms of terminal SePh and PPh3 ligands. The compound II is a six‐membered ring with alternating Hg and Se atoms in the chair conformation. Two DMSO molecules occupy positions below and above the [Hg3Se3] ring with the oxygen atoms directed to the centre of the ring.  相似文献   

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[(Cp4i Rh)2(μ‐Cl)3] [Rh(CO)2Cl2] (Cp4i = tetraisopropyl‐cyclopenta‐dienyl) has been prepared and its crystal is in the space group of Pbar with a= 0.9417 (8), b = 1.4806 (3), c = 1.5062 (2) nm, a = 92.980(10), β = 97.42(3), γ = 93.98 (3)°, V = 2.0735(18) nm3 and Z = 2. The crystal structure consists of a cation of [(η5‐Cp4i) Rh (III)(μ‐Cl)3 Rh (III) (η5‐Cp4i)]+ and an anion of [Rh (I) (CO)2 Cl2]. The two bulky tetraisopropylcyclopentadienyl ligands are in the ecliptic conformation with angle of 10.19° between two cyclopentadienyl ring planes.  相似文献   

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Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], and [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] [Ru3Rh(CO)73‐H)(μ‐PtBu2)2(tBu2PH)(μ‐Cl)2] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) Å3. The reaction of 4 with dppm (Ph2PCH2PPh2) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 Å3. Moreover single crystals of [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P21/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) Å3.  相似文献   

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Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)2]3[Co32-NHMes)3Cl6] (1), [Li(DME)3]2[Co184-NPh)33-NPh)12Cl3] (2), [Li(DME)3]2[Co64-NPh)(μ2-NPh)6(PPh2Et)2] (3), and [Li(THF)4][Co83-NPh)62-NPh)3(PPh3)2] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li2NPh leads to an amido-bridged multinuclear complex [Li(THF)2]3[Co32-NHMes)3Cl6] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)3]2[Co184-NPh)33-NPh)12Cl3] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)3]2[Co64-NPh)(μ2-NPh)6(PPh2Et)2] ( 3 ) and [Li(THF)4][Co83-NPh)62-NPh)3(PPh3)2] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.  相似文献   

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[Fe2sb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthesis, X‐ray Crystal Structure and Isomerization Na[Fe2(μ‐CO)(CO)6(μ‐PtBu2)] ( 1 ) reacts with [NO][BF4] at —60 °C in THF to the nitrosyl complex [Fe2(CO)6(NO)(μ‐PtBu2)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes [Fe2(CO)5(NO)L(μ‐PtBu2)], L = PPh3, ( 3a ); η‐dppm (dppm = Ph2PCH2PPh2), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound [Fe2(CO)4(NO)(μ‐PtBu2)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers [Fe2sb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐dppm)] ( 4a ) and [Fe2(CO)4(μ‐NO)(μ‐PtBu2)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields.  相似文献   

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Conclusions The-dienyl complexes are formed when tetrakis (trifluoromethyl)allene is reacted with dicarbonyltriphenylphosphine--cyclopentadienylmolybdate and dicarbonyltriphenylphosphine--cyclopentadienyltungstate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 681–683, March, 1978.  相似文献   

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The reaction of the K2[Fe3Q(CO)9] clusters (Q = Se or Te) with Rh2(CO)4Cl2 under mild conditions is accompanied by complicated fragmentation of cores of the starting clusters to form large heteronuclear cluster anions. The [PPh4][Fe4Rh3Se2(CO)16] and [PPh4]2[Fe3Rh4Te2(CO)15] compounds were isolated by treatment of the reaction products with tetraphenylphosphonium bromide. The structures of the products were established by X-ray diffraction. In both compounds, the core of the heteronuclear cluster consists of two octahedra fused via a common Rh3 face. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 775–778, May, 2006.  相似文献   

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