In chemistry, a metalloborane is a compound that contains one or more metal atoms and one or more boron hydride. These compounds are related conceptually and often synthetically to the boron-hydride clusters by replacement of BHn units with metal-containing fragments. Often these metal fragments are derived from metal carbonyls or cyclopentadienyl complexes. Their structures can often be rationalized by polyhedral skeletal electron pair theory. The inventory of these compounds is large, and their structures can be quite complex. [2] [3]
Two simple examples are B4H8Fe(CO)3 and B4H8Co(C5H5). The MB4 cores (M = Fe or Co) of these two compounds adopt structures expected for nido 5-vertex clusters. The iron compound is produced by reaction of diiron nonacarbonyl with pentaborane. B4H8Fe(CO)3 and cyclobutadieneiron tricarbonyl have similar structures.
Even greater in scope than metalloboranes are metallacarboranes. These cages have carbon vertices, often CH, in addition to BH and M vertices. [2] A well-developed class of metallacarboranes are prepared from dicarbollides, anions of the formula [C2B9H11]2-. These anions function as ligands for a variety of metals, often forming sandwich complexes. [5]
Some metalloboranes are derived by the metalation of neutral carboranes. Illustrative are the six-and seven-vertex cages prepared from closo-C2B3H5. Reaction of this carborane with iron carbonyl sources gives closo Fe- and Fe2-containing products, according to these idealized equations: [6]
A further example of insertion into a closo carborane is the synthesis of the yellow-orange solid closo-1,2,3-(CO)3FeC2B4H6:
A closely related reaction involves the capping of an anionic nido carborane C2B4H−7
The last reaction is worked up with acid and air.
A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5H−
5, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.
Boron hydride clusters are compounds with the formula BxHy or related anions, where x ≥ 3. Many such cluster compounds are known. Common examples are those with 5, 10, and 12 boron atoms. Although they have few practical applications, the borane hydride clusters exhibit structures and bonding that differs strongly from the patterns seen in hydrocarbons. Hybrids of boranes and hydrocarbons, the carboranes are also well developed.
Decaborane, also called decaborane(14), is the inorganic compound with the chemical formula B10H14. It is classified as a borane and more specifically a boron hydride cluster. This white crystalline compound is one of the principal boron hydride clusters, both as a reference structure and as a precursor to other boron hydrides. It is toxic and volatile, giving off a foul odor, like that of burnt rubber or chocolate.
Carboranes are electron-delocalized clusters composed of boron, carbon and hydrogen atoms. Like many of the related boron hydrides, these clusters are polyhedra or fragments of polyhedra. Carboranes are one class of heteroboranes.
In chemistry the polyhedral skeletal electron pair theory (PSEPT) provides electron counting rules useful for predicting the structures of clusters such as borane and carborane clusters. The electron counting rules were originally formulated by Kenneth Wade, and were further developed by others including Michael Mingos; they are sometimes known as Wade's rules or the Wade–Mingos rules. The rules are based on a molecular orbital treatment of the bonding. These rules have been extended and unified in the form of the Jemmis mno rules.
Triiron dodecarbonyl is the organoiron compound with the formula Fe3(CO)12. It is a dark green solid that sublimes under vacuum. It is soluble in nonpolar organic solvents to give intensely green solutions. Most low-nuclearity clusters are pale yellow or orange. Hot solutions of Fe3(CO)12 decompose to an iron mirror, which can be pyrophoric in air. The solid decomposes slowly in air, and thus samples are typically stored cold under an inert atmosphere. It is a more reactive source of iron(0) than iron pentacarbonyl.
Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H−-like character (e.g., ZnH2).
Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005 is the 2005 version of Nomenclature of Inorganic Chemistry. It is a collection of rules for naming inorganic compounds, as recommended by the International Union of Pure and Applied Chemistry (IUPAC).
Sodium cyclopentadienide is an organosodium compound with the formula C5H5Na. The compound is often abbreviated as NaCp, where Cp− is the cyclopentadienide anion. Sodium cyclopentadienide is a colorless solid, although samples often are pink owing to traces of oxidized impurities.
Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.
Iron tetracarbonyl dihydride is the organometallic compound with the formula H2Fe(CO)4. This compound was the first transition metal hydride discovered. The complex is stable at low temperatures but decomposes rapidly at temperatures above –20 °C.
In organometallic chemistry, a dicarbollide is an anion of the formula [C2B9H11]2-. Various isomers exist, but most common is 1,2-dicarbollide derived from ortho-carborane. These dianions function as ligands, related to the cyclopentadienyl anion. Substituted dicarbollides are also known such as [C2B9H10(pyridine)]− (pyridine bonded to B) and [C2R2B9H9]2- (R groups bonded to carbon).
In chemistry, the Jemmis mno rules represent a unified rule for predicting and systematizing structures of compounds, usually clusters. The rules involve electron counting. They were formulated by E. D. Jemmis to explain the structures of condensed polyhedral boranes such as B20H16, which are obtained by condensing polyhedral boranes by sharing a triangular face, an edge, a single vertex, or four vertices. These rules are additions and extensions to Wade's rules and polyhedral skeletal electron pair theory. The Jemmis mno rule provides the relationship between polyhedral boranes, condensed polyhedral boranes, and β-rhombohedral boron. This is similar to the relationship between benzene, condensed benzenoid aromatics, and graphite, shown by Hückel's 4n + 2 rule, as well as the relationship between tetracoordinate tetrahedral carbon compounds and diamond. The Jemmis mno rules reduce to Hückel's rule when restricted to two dimensions and reduce to Wade's rules when restricted to one polyhedron.
The dodecaborate(12) anion, [B12H12]2−, is a borane with an icosahedral arrangement of 12 boron atoms, with each boron atom being attached to a hydrogen atom. Its symmetry is classified by the molecular point group Ih.
Heteroboranes are classes of boranes in which at least one boron atom is replaced by another elements. Like many of the related boranes, these clusters are polyhedra and are similarly classified as closo-, nido-, arachno-, and hypho-, according to the so-called electron count. Closo- represents a complete polyhedron, while nido-, arachno- and hypho- stand for polyhedrons that are missing one, two and three vertices.
ortho-Carborane is the organoboron compound with the formula C2B10H12. The prefix ortho is derived from ortho. It is the most prominent carborane. This derivative has been considered for a wide range of applications from heat-resistant polymers to medical applications. It is a colorless solid that melts, without decomposition, at 320 °C
Metal cluster compounds are a molecular ion or neutral compound composed of three or more metals and featuring significant metal-metal interactions.
In organoiron chemistry, a ferrole is a type of diiron complex containing the (OC)3FeC4R4 heterocycle that is pi-bonded to a Fe(CO)3 group. These compounds have Fe-Fe bonds (ca. 252 pm) and semi-bridging CO ligands (Fe-C distances = 178, 251 pm). They are typically air-stable, soluble in nonpolar solvents, and red-orange in color.
The stabilization of bismuth's +3 oxidation state due to the inert pair effect yields a plethora of organometallic bismuth-transition metal compounds and clusters with interesting electronics and 3D structures.
Disulfidobis(tricarbonyliron), or Fe2(μ-S2)(CO)6, is an organometallic molecule used as a precursor in the synthesis of iron-sulfur compounds. Popularized as a synthetic building block by Dietmar Seyferth, Fe2(μ-S2)(CO)6 is commonly used to make mimics of the H-cluster in [FeFe]-hydrogenase. Much of the reactivity of Fe2(μ-S2)(CO)6 proceeds through its sulfur-centered dianion, [Fe2(μ-S)2(CO)2]2-.