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  • Articles  (49)
  • Articles: DFG German National Licenses  (49)
  • Crystal Structure  (40)
  • Synthesis  (29)
  • 550 - Earth sciences
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 616 (1992), S. 141-144 
    ISSN: 0044-2313
    Keywords: Crystal structure ; Synthesis ; Thermolysis, Lanthanides ; Ternary ammonium nitrates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Structure, and Thermolysis of the (NH4)3[M2(NO3)9] (M = La—Gd)The ternary ammonium nitrates (NH4)3[M2(NO3)9] (M = La-Gd) are obtained as single crystals from a solution of the respective sesquioxides in a melt of NH4NO3 and sublimation of the excess NH4NO3. In the crystal structure of (NH4)3[Pr2(NO3)9] (cubic, P4332, Z = 4, a = 1 377.0(1) pm, R = 0.038, Rw = 0.023) Pr3+ is surrounded by six bidentate nitrate ligands of which three are bridging to neighbouring Pr3+ ions. This results in a branched folded chain, held together by the NH4+ ions which occupy cavities in the structure. (NH4)3[Pr2(NO3)9] is the first intermediate product of the thermal decomposition of (NH4)2[Pr(NO3)5(H2O)2] · 2H2O.
    Notes: Die ternären Ammoniumnitrate (NH4)3[M2(NO3)9] (M = La—Gd) erhält man in Form von Einkristallen durch Auflösen der entsprechenden Sesquioxide in einer Schmelze von NH4NO3 und Entfernen des Überschusses durch Sublimation. Die Strukturanalyse am Beispiel von (NH4)3[Pr2(NO3)9] (kubisch, P4332, Z = 4; a = 1377,0(1) pm; R = 0,038; Rw = 0,023) zeigt, daß Pr3+ von sechs zweizähnigen Nitratliganden umgeben ist, von denen drei jeweils zu einem weiteren Pr3+-Ion verbrücken. Dadurch entsteht eine verzweigte, gefaltete Kette. Sie wird durch NH4+-Ionen zusammengehalten, die sich in Hohlräumen befinden. (NH4)3[Pr2(NO3)9] stellt die erste Stufe beim thermischen Abbau von (NH4)2[Pr(NO3)9(H2O)2] · 2H2O dar.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 513-516 
    ISSN: 0044-2313
    Keywords: Synthesis ; Crystal Structure ; Lanthanides ; Ternary Lithium Nitrates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of the First Anhydrous Ternary Lithium Nitrates of the Lanthanides, Li2[M(NO3)5] (M = La, Pr—Eu).Single crystals of the ternary lithium nitrates of the lanthanides, Li2[M(NO3)5] (M = La, Pr—Eu), are obtained by dissolving the respective anhydrous nitrate, previously obtained by dehydration of M(NO3)3 · 6 H2O at 180°C under vacuum, in a melt of LiNO3. In the crystal structure of Li2[Pr(NO3)5] (orthorhombic, Pnnm, Z = 4, a = 899.6(2), b = 1 052.7(2), c = 1 178.6(2)pm; R = 0.072, Rw = 0.034) there are two crystallographically different Pr3+ ions, each surrounded by six bidentate nitrate ligands. One nitrate group is bridging between Pr1 and Pr2 resulting in a winded chain, ∞1[(O2/2NO2/1)Pr1(NO3)4(O2/2NO2/1)Pr2(O2/2NO2/1)(NO3)4]5-, running along [010]. The chains are packed hexagonally and held together by lithium ions. The coordination polyhydron of Li+ may be described as a bicapped trigonal prism.
    Notes: Einkristalle der ternären Nitrate der Lanthanide vom Typ Li2[M(NO3)5] (M = La, Pr—Eu) erhält man durch Auflösen der zuvor bei 180°C unter Vakuum entwässerten Hydrate M(NO3)3 · 6 H2O in einer Lithiumnitrat-Schmelze. Die Röntgenstrukturanalyse am Beispiel von Li2[Pr(NO3)5] (orthorhombisch, Pnnm, Z = 4; a = 899,6(2); b = 1 052,7(2); c = 1 178,6(2)pm; R = 0,072; Rw = 0,034) zeigt, daß zwei kristallographisch verschiedene Pr3+ vorliegen, die von jeweils sechs zweizähnigen Nitratliganden umgeben sind. Eine Nitratgruppe verbrückt zwischen Pr1 und Pr2, so daß sich eine gewundene Kette gemäß ∞1[(O2/2NO2/1)Pr1(NO3)4(O2/2NO2/1)Pr2(O2/2NO2/1)(NO3)4]5- ergibt, die längs [010] verläuft. Die Kettenstränge sind gemäß einer hexagonalen Stabpackung angeordnet und werden durch Li+-Ionen zusammengehalten. Die Koordination um Li+ kann als zweifach bekapptes trigonales Prisma beschrieben werden.
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  • 3
    ISSN: 0044-2313
    Keywords: Rare Earth Elements ; Halides ; Clusters ; Cesium Scandium Chloride Carbide ; Cesium Praseodymium Iodide Dicarbide ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cs4[Sc6C]Cl13 and Cs4[Pr6(C2)]I13  -  Two Examples for the Missing Link in the Connectivity of [M6Z]X12iX6a Building UnitsCs4[Sc6C]Cl13 (tetragonal, I41/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, Rw = 0.026) and Cs4[Pr6(C2)]I13 (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, Rw = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl3 and PrI3, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc6C] and [Pr6(C2)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xi and 6 Xa; X = Cl or I). The connection is carried out via the motif [M6Z]X8iX4/21-aX4/2a-1X2/2a-a (M = Sc and Pr; Z = C and C2, respectively) and is thereby the missing link of the motifs of connection for the composition Ax[M6Z]X13. Analogous interconnection of [TiO6] octahedra is found in the anatase-type of structure of TiO2.
    Notes: Cs4[Sc6C]Cl13 (tetragonal, I41/amd; a = 1 540,5(4); c = 1 017,9(7) pm; c/a = 0,661; Z = 4; R = 0,038; Rw = 0,026 und Cs4[Pr6(C2)]I13 (a = 1 804,9(3); c = 1 259,5(3) pm; c/a = 0,698; R = 0,106; Rw = 0,068) werden bei der metallothermischen Reduktion von ScCl3 bzw. PrI3 mit Caesium in Gegenwart von Kohlenstoff in verschweißten Tantalampullen in Form von grünschwarzen bzw. blauschwarzen, messingglänzenden Einkristallen erhalten. Die weitgehend isotypen Kristallstrukturen enthalten isolierte [Sc6C]- bzw. [Pr6(C2)]-Cluster, die von 18 Halogenid-Ionen (X-, 12 Xi und 6 Xa; X = Cl bzw. I) umgeben sind. Die Verknüpfung erfolgt gemäß dem Motiv [M6Z]X8iX4/21-aX4/2a-1X2/2a-a (M = Sc bzw. Pr; Z = C bzw. C2) und stellt damit ein noch unbekanntes Verknüpfungsmuster für Verbindungen der Zusammensetzung Ax[M6Z]X13 dar, das jenem der [TiO6]-Oktaeder in der Anatas-Struktur von TiO2 entspricht.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1527-1531 
    ISSN: 0044-2313
    Keywords: Terbium Cluster ; [Tb10(C2)2] ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cs3[Tb10(C2)2]Cl21, A New Formula and Structure Type with Isolated Dimeric ClustersCs3[Tb10(C2)2]Cl21 is obtained via the metallothermic reduction of TbCl3 with caesium in the presence of graphite as black single crystals. The crystal structure (monoclinic, C2/c, Z = 4; a = 2318.72(13); b = 1245.8(9); c = 1502.0(13) pm; β = 98.13(6)°; R = 0.089; Rw = 0.049) contains dimeric clusters that are built from two octahedra connected via one common edge and filled with C2 units. These isolated [Tb10(C2)2] clusters are surrounded by 26 chloride ligands which are then connected via i - a and a - a bridges in a way that voids for Cs+ of coordination number 10 are formed.
    Notes: Cs3[Tb10(C2)2]Cl21 entsteht bei der metallothermischen Reduktion von TbCl3 mit Caesium in Gegenwart von Graphit in Form schwarzer Einkristalle. Die Kristallstruktur (monoklin, C2/c, z = 4; a = 2318,72(13); b = 1245,8(9); c = 1502,0(13) pm; β = 98,13(6)°; R = 0,089; Rw = 0,049) enthält dimere Cluster, die aus zwei über eine gemeinsame Kante verknüpften und durch zwei C2-Hanteln aufgefüllten Oktaedern gebildet werden. Die isolierten [Tb10(C2)2]-Cluster sind von insgesamt 26 Cl- umgeben und durch i - a- bzw. a - a-Brücken so miteinander verknüpft, daß für die Cs+ Lücken der Koordinationszahl 10 verbleiben.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1493-1495 
    ISSN: 0044-2313
    Keywords: Synthesis ; Crystal structure ; Crown ether ; Lanthanides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [La2I2(OH)2(dibenzo-18-crown-6)2]I(I3), a Cationic Dimeric in-cavity Complex with Iodide and Triiodide as AnionsSingle crystals of [La2I2(OH)2(dibenzo-18-crown-6)2]I(I3) are obtained from the reaction of LaI3 and dibenzo-18-crown-6 in acetonitrile. The crystal structure monoclinic, C2/m, Z = 4, T = 293 [100] K, a = 2179(3) [2162.3(3)], b = 1070.3(3) [1069.6(1)], c = 1118.2(3) [1110.6(1)] pm, β = 93.1(1) [92.83(1)]°, R1 = 0.0601 [0.0411], wR2 = 0.1449 [0.1014] contains hydroxide-bridged cationic dimers and iodide as well as triiodide as anions.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1393-1398 
    ISSN: 0044-2313
    Keywords: Rare Earth Fluorides ; Crystal Structure ; Ammonium Fluorides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of NH4DyF4. Further Fluorides NH4MF4 (M = La—Tb)
    Notes: Die Fluoride NH4MF4 (M = La—Dy) entstehen bei der Umsetzung der Metalle M mit N2H6F2 bei Temperaturen zwischen 80 und 350°C in verschweißten Monelampullen. Es werden in Abhängigkeit vom Selten-Erd-Element und von der Reaktionstemperatur drei Strukturen beobachtet: Die Kristallstruktur der Form I wurde anhand von Einkristallen von NH4DyF4 aufgeklärt [orthorhombisch, Pbcm (Nr. 57), Z = 4; a = 852,10(7) pm, b = 722,54(8) pm, c = 626,28(12) pm]; die bei niedrigen Temperaturen hergestellten Fluoride NH4MF4 (M = Ce—Tb) sind isotyp. Bei höheren Temperaturen treten die Formen II [für M = La—Nd; orthorhombisch (?), Z = 8] bzw. III [M = Eu—Tb, geordnete Überstruktur zum CaF2-Typ, analog TlGdF4, tetragonal, P4/m (?), Z = 16] auf.The fluorides NH4MF4 (M = La—Dy) are obtained through the reaction of the metals M with N2H6F2 at temperatures between 80 and 350°C in sealed Monel ampoules. Dependent upon the rare-earth element M and the reaction temperature three crystal structures are observed: The crystal structure of modification I was determined from single crystal data of NH4DyF4 [orthorhombic, Pbcm (no. 57), Z = 4; a = 852.10(7) pm, b = 722.54(8) pm, c = 626.28(12) pm]; the fluorides NH4MF4 (M = Ce—Tb) obtained at fairly low temperatures are isotypic. At higher temperatures the modifications II [for M = La—Nd; orthorhombic (?), Z = 8] and III [M = Eu—Tb, ordered superstructure of the CaF2 type, analogous to TlGdF4, tetragonal, P4/m (?), Z = 16] are observed.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 200-204 
    ISSN: 0044-2313
    Keywords: Alkaline Earth ; Praseodym ; Iron Oxide ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Ba6Pr2Fe4O15, Ba5SrPr2Fe4O15 and Ba5CaPr2Fe4O15Ba6Pr2Fe4O15 (I), Ba5SrPr2Fe4O15 (II), and Ba5CaPr2Fe4O15 (III) have been prepared by high temperature CO2-LASER techniques. (I)-(III) crystallize isotypic to the Ba6Ln2Al4O15 type, space group C6v4-P63mc, (I): a = 11.808(2), c = 6.894(5), Z = 2. Typical features of the crystal structure are face shared MO6 octahedra (M = Ba or Ba/Sr, Ba/Ca) and a statistical distribution of Ba and Pr in a ratio of 1 : 2 within double capped trigonal prisms of oxygen. Fe shows tetrahedral as well as octahedral coordination by oxygen. Calculation of coulomb terms of lattice energy indicate the stabilization of Pr3+ beside Fe3+ by the Ba6Ln2Al4O15 type.
    Notes: Ba6Pr2Fe4O15 (I), Ba5SrPr2Fe4O15 (II) und Ba5CaPr2Fe4O15 (III) wurden mit Hochtemperatur-CO2-LASER-Technik dargestellt. (I)-(III) kristallisieren mit hexagonaler Symmetrie, Raumgruppe C6V4-P63mc, (I): a = 11.808(2), c = 7,036(4) Å; (II): a = 11.689(2), c = 6.954(2) Å; (III): a = 11.602(6), c = 6.894(5) Å, Z = 2. Charakteristische Eigenschaften dieser Kristallstruktur sind flächenverknüpfte MO6-Oktaeder (M = Ba oder Ba/Sr, Ba/Ca) und eine statistische Verteilung von Ba und Pr im Verhältnis 1 : 2 in einem zweifach überkappten trigonalen Sauerstoffprisma. Fe zeigt sowohl tetraedrische als auch oktaedrische Sauerstoffkoordination. Berechnungen der Coulomb-Terme zur Gitterenergie deuten an, daß durch den Ba6Ln2A4O15-Typ Pr3+ neben Fe3+ stabilisiert wird.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 791-795 
    ISSN: 0044-2313
    Keywords: Lithium Niobium Chloride ; Niobium Cluster ; Synthesis ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zweidimensionale Netzwerke in der Struktur von Li2[Nb6Cl16]Li2[Nb6Cl16] wurde aus Nb-Pulver, NbCl5 und LiCl in Quarzglasampullen bei 700°C hergestellt. Die anhand von Einkristall-Röntgendaten verfeinerte Kristallstruktur ist orthorhombisch, Raumgruppe Cmca (Nr. 64), mit Z = 4 und Gitterkonstanten von a = 1274.7(1) pm, b = 1318.5(1) pm, c = 1341.1(2) pm. Die Verfeinerung aller Atompositionen ergab R1 = 0.031 (basierend auf F-Werten) und wR2 = 0.081 (basierend auf F2-Werten). Die Struktur enthält Schichten aus [Nb6Cl12i]2+ mit äußeren Cla-a-Liganden, die vier Ecken jedes oktaedrischen Niobclusters in Schichten verknüpfen, plus zwei terminale Cla-Liganden an jedem Niobcluster, entsprechend [Nb6Cl12iCl4/2a-aCl2a]2-. Das gleiche Verknüpfungsmuster liegt in binären Mo6X12-Halogeniden vor, die jedoch acht innere Halogenliganden besitzen (Mo6Cl8i). Gewinkelte Nb-Cla-a-Nb Brücken (159°) zwischen benachbarten Niobclustern korrespondieren mit Verdrehungen der [Nb6Cl16]2--Einheiten innerhalb der Schichten, wodurch zwei Li+ verzerrt trigonal-bipyramidale Lücken besetzen.
    Notes: Li2[Nb6Cl16] has been synthesized from the reaction of Nb powder, NbCl5 and LiCl in sealed silica tubes at 700°C. The structure, as determined by single-crystal X-ray diffraction, is orthorhombic, space group Cmca (no. 64) with Z = 4 and has lattice parameters a = 1274.7(1) pm, b = 1318.5(1) pm, c = 1341.1(2) pm. The refinement of all atomic positions yielded Rl = 0.031 (based on F values) and wR2 = 0.081 (based on F2 values). The structure contains layers formed by [Nb6Cl2i]2+ with outer Cla-a ligands that bridge four vertices of each octahedral niobium cluster into sheets, plus two terminal Cla ligands of each cluster, to be described as [Nb6Cl12iCl4/2a-aCl2a]2-. The same connectivity pattern is present for binary Mo6X12 halides, containing eight inner halide ligands (Mo6Cl8i). Non-linear Nb-Cla-a-Nb bridges (159°) correspond with intra-layer rotations of [Nb6Cl16]2 units and thereby accommodate two Li+ in distorted trigonal - bipyramidal voids.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 981-984 
    ISSN: 0044-2313
    Keywords: Samarium ; Iodide ; Crown Ether Complexes ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of the Monomeric in-cavity Complex [SmI3(dibenzo-18-crown-6)]Red crystals of [SmI3(dibenzo-18-crown-6)] are obtained by reaction of SmI3 with dibenzo-18-crown-6-ether in acetonitrile. The crystal structure (tetragonal, P43212, Z = 4; a = 962.7(1) pm, c = 2690.0(3) pm; R1 = 0.041; wR2 = 0.101) contains the neutral molecules [SmI3(dibenzo-18-crown-6)]. Distorted triangular SmI3 units are surrounded perpendicularly by one molecule of the crown ether so that a coordination number of 9 results for Sm3+ (three iodide ions and the six oxygen atoms of the crown ether).
    Notes: Bei der Umsetzung von SmI3 mit Dibenzo-18-Krone-6-Ether in Acetonitril erhält man rötliche Kristalle von [SmI3(Dibenzo-18-Krone-6)]. Die Kristallstruktur (tetragonal, P43212, Z = 4; a = 962,7(1) pm, c = 2690,0(3) pm; R1 = 0,041; wR2 = 0,101) ist aus neutralen Molekülen der Zusammensetzung [SmI3(Dibenzo-18-Krone-6)] aufgebaut: Verzerrt trigonal-planare SmI3-Einheiten sind von einem Molekül des Kronenethers umgeben, so daß Sm3+ die Koordinationszahl 9 hat (durch drei Iodid-Ionen und die sechs Sauerstoffatome des Kronenethers).
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  • 10
    ISSN: 0044-2313
    Keywords: Heterodinuclear Cyclooctatetraene Complexes ; Synthesis ; Crystal Structure ; ESR Spectrum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kooperative Wirkung in π-Ligand-verbrückten Zweikernkomplexen. XII. Gemischtkernige elektronenarme μ-Cyclooctatetraen-Zweikernkomplexe mit CrFe-und CrCo-KombinationenDie synfacialen gemischtkernigen μ-Cot-Zweikernkomplexe [(CpCr)(CpM)]μ-Cot (M = Fe, 3; M = Co, 4) (Cp = Cyclopentadienyl; Cot = Cyclooctatetraen) werden in thermischen Reaktionen aus der einkernigen Sandwichverbindung CpCr(n6-Cot) und CpMLn [M = Fe, Ln = Benzol (Bz); M = Co, Ln = (C2H4)2] gebildet. 3 besitzt zwei ungepaarte Elektronen, während 4 mit nur einem ungepaarten Elektron SSR-ak-tiv ist. Aufgrund der Molekülstruktur von 3 und den ESR-Daten von 4 kann gefolgert werden, daß die ungepaarten Elektronen dieser Produkte hauptsächlich auf den Cr-Zentren lokalisiert sind. Daraus ergibt sich eine enge elektronische Verwandtschaft zwischen den hetero-dinuklearen Verbindungen 3 und 4 und den einkernigen Sandwichverbindungen Chromocen beziehungsweise CpCrBz.
    Notes: The synfacial heterodinuclear μ-Cot complexes (Cot = cyclooctatetraene) [(CpCr) (CpM)]μ-Cot (Cp = cyclopentadienyl; M = Fe, 3; M = Co, 4) are formed in a thermal reaction of the mononuclear mixed sandwich compound CpCr(n6-Cot) and CpMLn [M = Fe, Ln = benzene (Bz); M = Co, Ln = (C2H4)2]. 3 possesses two unpaired electrons whereas 4 has only one unpaired electron and is ESR active. From the molecular structure of 3 and from the ESR data of 4 it can be deduced that the unpaired electrons are localized at the Cr centers predominantly forcing a close electronical relation between the heterodinuclear compounds 3 and 4 and the mononuclear sandwich complexes chromocene and CpCrBz, respectively.
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