Reactions of cyclopentadienylmolybdenum compounds with bismuth alkoxides

Hunger, Marc; Limberg, Christian; Kaifer, Elisabeth; Rutsch, Peter

doi:10.1016/s0022-328x(01)01303-1

Cited by 35 publications

(23 citation statements)

References 44 publications

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“…In contrast to the structure of I, which contains a crystallographic C 2 axis, the structure of 1 is asymmetric with two different MoÀBi bond lengths (MoÀBi1 2.897(2) and MoÀ Bi2 2.851(1) ). Both are comparable to those found in the known MoBi compounds, [2][3][4][5] one of them being almost identical to the corresponding bond lengths found in I (2.8551(9) ). [1] As in I the BiÀBi distance (3.526(2) ; 3.487(2) in I)) is too long to be interpreted in terms of a BiÀBi bond, but considering the Bi-Mo-Bi angle of only 75.66(4)8 there cannot be significant repulsive forces between the two Bi(OR) 2 1:2 (as required for the formation of 1) to 1:1.…”

Section: Resultssupporting

confidence: 84%

“…Figure 8 summarises all these theoretical results concerning the kinetic and thermodynamic situation in the system which may serve to rationalise the very peculiar observation that the reaction between [Cp 2 MoH 2 ]/[Bi(OtBu) 3 ] first of all leads to pure crystals of 3 in good yields, while on setting aside the mother liquor after separation of the first bunch of crystals a 1:1 mixture of 3 and 4 is isolated.…”

mentioning

confidence: 67%

“…[2] To obtain structural information about 1, crystals were grown at À30 8C from hexane and investigated by a single-crystal X-ray diffraction study.…”

Section: Resultsmentioning

confidence: 99%

“…This unusual arrangement is made possible through nonlinear orbital overlaps, that is, "bent bonds" between Bi and C atoms. [1] Parallel to the investigation outlined above we have studied the parent system with unsubstituted cyclopentadienyl rings, that is, [Cp 2 MoH 2 ]/[Bi(OtBu) 3 ]. Surprisingly, this study proved to be notably more demanding, both with regard to synthetic and analytical aspects: It turned out, that changing from the methylcyclopentadienide to the parent cyclopentadienide ligand has a significant chemical influence on the system, for example, on 1) the courses of some of the [ 3 ligand.…”

Section: Introductionmentioning

confidence: 99%

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“Bent Bonds” between Bismuth and Carbon Atoms as a Result of CH Activation in MoBi Complexes

Roggan

Schnakenburg

Limberg

et al. 2004

Chemistry A European J

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The reaction of molybdocenedihydride with two equivalents of [Bi(OtBu)(3)] proceeds via alcohol elimination and provides the compound [Cp(2)Mo{Bi(OtBu)(2)}(2)] (1), which contains two Mo--Bi metal bonds, in good yields. If the two reagents are employed in a 1:1 ratio continuative condensation reactions occur. These initially lead to [{Cp(2)Mo}(2){mu-Bi(OtBu)}(2)] (2), which, however, is very unstable in solution and decomposes via additional alcohol elimination: Complex-induced proximity effects facilitate the cleavage of C--H bonds within the cyclopentadienyl ligands by the residual alkoxide ligands, so that spontaneously two further equivalents of alcohol are released, thereby yielding two isomeric compounds 3 and 4 with Cp ligands bridging Mo--Bi metal bonds: The first isomer (3) contains two mu(2)-eta(5):eta(1)-C(5)H(4) ligands, the second isomer (4) contains one bridging mu(3)-eta(5):eta(1):eta(1)-C(5)H(3) ligand. The binding of these ligands to molybdenum and bismuth atoms at the same time is made possible through "bent bonds" between the bismuth and certain carbon centres. These unusual bonding situations were analysed by means of calculations based on density functional theory (DFT), the atoms in molecules (AIM) theory, natural bond order (NBO) considerations and the electron localisation function (ELF). According to the results the bonds can be understood in terms of carbanionic centres interacting with bismuth cations (i.e. closed-shell interactions). The formation of these bonds and the thermodynamics/kinetics involved on going from 2 to 3 and 4 were also studied by theoretical methods, so that the product formation is rationalised. The crystal structures of all four new compounds were determined. These structures but also the properties and mechanisms of formation are discussed against the background of the corresponding results obtained while studying the system [(Me)Cp(2)MoH(2)]/[Bi(OtBu)(3)].

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Section: Resultssupporting

confidence: 84%

mentioning

confidence: 67%

“…[2] To obtain structural information about 1, crystals were grown at À30 8C from hexane and investigated by a single-crystal X-ray diffraction study.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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“Bent Bonds” between Bismuth and Carbon Atoms as a Result of CH Activation in MoBi Complexes

Roggan

Schnakenburg

Limberg

et al. 2004

Chemistry A European J

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“…Surprisingly, the Cp1-Re3-Cp2 angle of 152.9(8) • (Cp-M-Cp is defined as the angle between the metalCp plane normals throughout this paper [14]) is comparable to that of the distorted rhenocene unit in 3 (156.40 (12) 3 ] systems we were able to show that the progress of the alcohol elimination sensitively depends on the nature of the residues R of the alkoxides employed [7 -13]. In case of hexafluoroiso-propyl residues, alcohol eliminations involving the Cp rings were suppressed [10]. 2 in the same solvent at ambient temperature.…”

Section: Complex Synthesis and Characterizationmentioning

confidence: 89%

Heterometallic Complexes with Rhenium- and Iron-Bismuth Bonds

Schiwon

Metzinger

Pfirrmann

et al. 2013

Zeitschrift Für Naturforschung B

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Bismuth: Inorganic Chemistry

Whitmire

2004

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This review presents findings from 420 references. Bismuth has a diverse chemistry from the properties of the element to those of its important solid‐state compounds and its varied coordination complexes. Bismuth is the heaviest stable element whose chemistry is dominated by the +3 oxidation state, but −3, +1, +2, and +5 oxidation numbers are also accessible. In contrast to the lighter pnictogens, very few inorganic bismuth(V) compounds have been reported. The best characterized of these is BiF 5 , which is a strongly oxidizing Lewis acid that readily forms the BiF 6 − ion in the presence of a variety of F− ion donors. In this review, the chemistry of bismuth is organized by compound classification. Included are sections on the properties of the element, its intermetallic compounds and important solid‐state materials such as the bismuth oxides, chalcogenides, and pnictides. Recent work has been directed toward production of elemental bismuth and key solid‐state compounds in nanoparticle form. The solid‐state materials have important applications including high TC superconductors, ferroelectric, and piezoelectric materials, oxide ion conductors, catalysts, thermoelectric materials, etc. In its reduced compounds with alkali and alkaline earth metals, bismuth forms a number of homometallic and heterometallic anionic Zintl ions showing Bi–Bi bonding and a strong tendency toward cluster formation. Cationic clusters in reduced halide species have been observed. Bi–Bi single and double bonds are known. Molecular compounds are discussed and organized by the donor elements coordinated to bismuth, including sections on amines and amides, alkoxides, carboxylates, thiolates, and halides. The halides along with Bi(NO 3 ) 3 · 5H2O are amongst the most common starting materials for synthesizing other bismuth complexes. The alkoxide and carboxylate complexes are subject to facile hydrolysis leading to a wide variety of oxo‐alkoxide and oxo‐carboxylate complexes. Particularly stable configurations for these oxo clusters are Bi 9 and Bi 38 . These latter two cluster sizes stabilized by salicylate ligands are good model compounds for the bismuth subcarboxylate compounds, which have found widespread medicinal usage. High coordination numbers ranging from two to nine are common and the Bi 3+ ion is well‐known for its high Lewis acidity. Despite its identity as a heavy metal, its compounds are generally nontoxic to humans and enjoy a wide application as antibacterial and antifungal agents. Aspects of the biological chemistry of bismuth compounds are surveyed. A rich chemistry of bismuth coordinated to organometallic transition metal fragments is well developed. Many Fe, Co, Ru, Os, and Re metal carbonyl complexes have been reported as well as cyclopentadienyl metal derivatives. Unusual structure and bonding patterns have been observed in these compounds that include representatives from Groups 6 through 11 as well as one organometallic lanthanide complex.

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Reactions of cyclopentadienylmolybdenum compounds with bismuth alkoxides

Cited by 35 publications

References 44 publications

“Bent Bonds” between Bismuth and Carbon Atoms as a Result of CH Activation in MoBi Complexes

“Bent Bonds” between Bismuth and Carbon Atoms as a Result of CH Activation in MoBi Complexes

Heterometallic Complexes with Rhenium- and Iron-Bismuth Bonds

Bismuth: Inorganic Chemistry

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