Organometallic oxides: the example of trioxo-(η5-pentamethylcyclopentadienyl)rhenium(VII)

doi:10.1016/S0277-5387(00)80866-9

Polyhedron

Volume 6, Issue 6, 1987, Pages 1165-1182

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The reactivity of halides of high valent groups 5 and 6 metals with oxygen and nitrogen organic donors and the parallelism with related chemistry of main groups
2023, Coordination Chemistry Reviews
Homoleptic halides of high-valent transition metals are acidic species possessing a strong affinity to N- and O-donors. The formation of coordination adducts with related organic ligands may be a prelude to subsequent activation reactions proceeding according to a variety of unconventional reactivity patterns. General aspects regarding the structure, the preparation, the properties and the salient reactivity of halides of elements belonging to groups 5, 6, 15 and (to a lesser extent) 16 of the periodic table, in an oxidation state of +V or + VI (when available), will be provided. Then, focusing on the most easily available metal halides (MX₅, M = Nb or Ta, X = F or Cl; MoCl₅ and WCl₆), the direct reactions with different categories of oxygen (carbonyl compounds, ethers, alcohols) and nitrogen (amines, imines, nitriles) organics will be discussed using a comparative approach, including the parallel chemistry of the pentahalides of group 15.
Unusual dimetallaborane cluster polyhedra and their skeletal bonding
2017, Coordination Chemistry Reviews
Citation Excerpt :
However, icosahedral PnM2B10H10 structures with surface MM triple bonds are also energetically accessible. The oblatocloso dirhenaboranes, although very interesting, are relatively difficult to synthesize not only because of the high cost of rhenium but also because of the complexity of the reported synthesis of the Cp∗ReCl4 precursor involving both Cp∗Re(CO)3 and Cp∗ReO3 as intermediates [65]. The analogous molybdenum and tungsten halide starting materials Cp∗MCl4 (M = Mo [66], W [67]) contain more abundant metals and are thus more readily available as precursors for metallaborane chemistry.
A variety of stable polyhedral dimetallaboranes have been synthesized exhibiting unusual polyhedral structures that challenge concepts of chemical bonding. In order to understand the underlying basis for such structures for dimetallaboranes and related species, comprehensive density functional studies have been performed on many such systems. This paper reviews the highlights of our recent work in this area. Systems discussed include the following: (1) The systems Cp₂Ni₂B_n₋₂H_n₋₂ (Cp = η⁵-C₅H₅) and Cp₂M₂C₂B_n₋₄H_n₋₂ (M = Co, Rh, Ir) having 2n + 2 Wadean skeletal electrons and exhibiting most spherical closo deltahedral structures; (2) The slightly hypoelectronic systems Cp₂M₂B_n₋₂H_n₋₂ (M = Co, Rh, Ir) and Cp₂Fe₂C₂B_n₋₄H_n₋₂ having only 2n Wadean skeletal electrons and in some cases, particularly the 10-vertex systems, exhibiting structures based on alternative isocloso deltahedra providing a degree 6 vertex for a metal atom; (3) Even more hypoelectronic dirhenaboranes and trirhenaboranes including flattened deltahedral oblatocloso structures exhibiting internal Re-Re bonding as well as closo and isocloso structures with short Re-Re edges suggesting formal triple and quadruple bonds; (4) Other hypoelectronic dimetallaboranes Cp₂M₂B_n₋₂H_n₋₂ with 2n − 2 Wadean skeletal electrons (M = Ru, Os) and 2n − 6 Wadean skeletal electrons (M = Mo, W); (5) Hydrogen-rich dimetallaboranes Cp₂M₂B_n₋₂H_n₊₂ (M = Ta, Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt; n = 5, 6, 7, 8), typically having the four “extra” hydrogen atoms bridging edges of an open polyhedral face.
Organorhenium dioxides as oxygen transfer systems: Synthesis, reactivity, and applications
2015, Coordination Chemistry Reviews
Citation Excerpt :
More diverse coordination chemistry is observed for Re(V)-dioxo derivatives compared with Re(VII)-trioxo derivatives due to electronic saturation and steric shielding by the cyclopentadiene ligand. In particular, the reactivity in the oxidation state Re(III) is similar to that of MDO [1,2,25,28,42–44]. Cp*ReO2 (12a) balances its electron deficiency by dimerization to [Cp*ReO(μ-O)]2 (17) in an analogous manner to MDO (see Scheme 8).
Organorhenium complexes are attracting interest because of their possible uses as deoxygenation catalysts in the refinement of lignocellulosic biomass such as lignin, carbohydrates, and sugar alcohols in the homogeneous phase. Furthermore, organorhenium compounds are known for their promising catalytic applications in the olefination of aldehydes, deoxygenation of epoxides, deoxydehydration of diols, hydrosilylation, and hydrogenation, where organorhenium dioxides (ORDs) are the key compounds in several cases. The wide substrate range of ORDs in mild reaction conditions is unrivaled by other catalysts. In this review, we summarize the roles of ORDs in molecular catalysis and the fundamental coordination chemistry of these compounds to facilitate a better understanding of the catalytic reaction steps. We provide comprehensive descriptions and visualizations of the generation, synthesis, and coordination chemistry of ORDs. ORDs are formed either by the reduction of common Re(VII) trioxides or by the oxidation of Re(III) compounds. Thus, we explain the strategies employed to allow the stabilization and isolation of very reactive dioxo-compounds. Their fundamental chemistry is based mainly on oxygen atom transfer reactions, thus we discuss possible reaction partners and conditions. In the second part of this review, we summarize all the known ORD-catalyzed reactions, thereby providing an overview and a mechanistic discussion of their catalytic applications. In particular, we review the roles and applications of ORDs in the refinement of biomass-derived compounds. The deoxydehydration of carbohydrates and sugar alcohols yields very useful synthetic building blocks, and thus we consider each carbon chain length from C₃ to C₆. In addition, we discuss catalytic CO bond cleavage in lignin model compounds.
Re(VII) and Tc(VII) trioxo complexes stabilized by tridentate ligands and their potential use as radiopharmaceuticals
2014, Coordination Chemistry Reviews
Citation Excerpt :
Tris(pyrazol-1-yl)alkanes with carbon instead of boron as bridging atom offer a higher hydrolytic stabilization, especially when used in vivo for radiopharmaceutical application. The complexes [{HC(pz)3}ReO3]+ (18) [52] and [{HC(pz*)3}ReO3]+ (19) [49] were synthesized from Re2O7 as well, whereas the remaining [ReO4]− served as counterion for the cationic species. The disadvantage of using Re2O7 as a starting material is the loss of one equivalent rhenium as counterion [71].
Tc(VII) and Re(VII) trioxo complexes are currently arousing interest because of their potential use as radiopharmaceuticals due to their hydrophilic character and stability in a biological environment. The radioactive isotopes ^99mTc and ¹⁸⁸Re are readily obtained from commercially available ⁹⁹Mo/^99mTc or ¹⁸⁸W/¹⁸⁸Re generators, respectively. Stabilization of the [MO₃]⁺ species is achieved by coordination of tridentate ligands (N, O, S and Pt donors). Herein, the various synthetic strategies to synthesize these complexes starting from M₂O₇, [MO₄]⁻, M(+V), M(+III) or M(+I) species are revised. The main structural features of the obtained distorted octahedral metal compounds are presented on the basis of their characterization by NMR and IR spectroscopy, and X-ray crystallography. Interestingly, the [MO₃]⁺ complexes undergo cycloaddition reactions, either to form the corresponding M(+V) diolate complexes via [3 + 2] cycloaddition, or carbene complexes via [2 + 2] cycloaddition. In this review we also comment on the few reported examples using [3 + 2] cycloaddition to label the trioxo compounds with bioactive molecules for their potential application as radiopharmaceuticals.
Flattened deltahedral structures and bridging hydrogen atoms in hypoelectronic dimolybdaboranes and ditungstaboranes
2014, Journal of Organometallic Chemistry
The following four Cp₂M₂B_n−2H_n−2 structure types (M = Mo, W) have been found in the low-energy structures using density functional theory: (1) Flattened oblatocloso deltahedra related to the experimentally known Cp₂Re₂B_n−2H_n−2 structures but not as severely flattened with intradeltahedral M–M (M = Mo, W) distances of ∼2.8 to ∼3.2 Å, which are 0.15–0.30 Å less than those in their Tc and Re counterparts; (2) Structures based on closo or isocloso deltahedra with short MM distances (M = Mo, W) of ∼2.4 to ∼2.6 Å along an edge corresponding to deltahedral surface metal–metal triple bonds; (3) Three 11-vertex deltahedral Cp₂M₂B₉H₉ structures (M = Mo, W) structures having two non-adjacent degree 6 vertices occupied by the metal atoms; (4) Two 8-vertex Cp₂M₂B₆H₆ structures with multiple degree 3 vertices arising from the capping of smaller deltahedra. In many of these structures one or two of the hydrogen atoms bridge M–B or B–B edges of the deltahedron.
Chemistry Surrounding Group 7 Complexes that Possess Poly(pyrazolyl)borate Ligands
2008, Advances in Organometallic Chemistry
This chapter reviews the chemistry observed with Group 7 (Mn, Tc, and Re) poly(pyrazolyl)borate complexes. The redox flexibility of these transition metals and the variability of poly(pyrazolyl) borate ligands have resulted in a wide range of chemistry. Poly(pyrazolyl)borate ligands support numerous complexes involving Group 7 transition metals. The flexibility of these ligands has allowed access to a range of oxidation states and geometries as well as provided Mn, Tc, and Re complexes with a diversity of reactivity. As a result of these attractive features, poly(pyrazolyl)borate ligands support a diversity of complexes, including coordination to all elements of groups 1 through 13 as well as some lanthanides and actinides. Transition metal complexes containing imido ligands are of interest due to their possible role in olefin aziridinations, metal-mediated metathesis of multiple bonds, ammoxidation reactions, C–H activation sequences as well as catalytic hydroamination of C–C multiple bonds. In addition, the chapter discusses about Rhenium, Manganese, and Technetium chemistry with respect to high oxidation as well as low oxidation state complexes.

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^☆: Communication 34 of the series “Multiple bonds between main group elements and transition metals”. Preceding paper: W. A. Herrmann, Ch. Hecht, E. Herdtweck and H.-J. Kneuper, Angew. Chem. (in press); Angew. Chem., Int. Ed. Engl. (in press).

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Polyhedron report number 21Organometallic oxides: the example of trioxo-(η5-pentamethylcyclopentadienyl)rhenium(VII)☆

First page preview

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

J. Organomet. Chem.

Chem. Ber.

Chem. Ber.

J. Chem. Soc. A

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

Inorg. Chem.

Chem. Eng. News

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

Nachr. Chem. Techn. Labor. (Weinheim/Germany)

J. Organomet. Chem.

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

J. Organomet. Chem.

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

Organometallics

J. Chem. Soc., Dalton Trans.

Organometallic

J. Organomet. Chem.

Inorg. Chem.

Angew Chem.

Angew. Chem., Int. Ed. Engl.

Organometallics

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Chem. Soc., Dalton Trans.

J. Chem. Soc., Dalton Trans.

Polyhedron report number 21
Organometallic oxides: the example of trioxo-(η⁵-pentamethylcyclopentadienyl)rhenium(VII)☆