Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Metallic monoboronyl compounds: Prediction of their structure and comparison with the cyanide analogues

“…A trinuclear complex of ruthenium capped by a BO ligand has also been synthesized . Other metal‐boronyl complexes have been predicted and theoretically studied, including different complexes of iron, cobalt, manganese, rhodium, palladium, and platinum . All these studies have provided detailed information about the interaction of different metals with the boronyl ligand, as well as about the role of boronyl as a potential ligand.…”

Density functional theory study of novel thioboronyl coupling reactions in unsaturated binuclear iron carbonyl derivatives

“…Using the reported synthesis of (Cy 3 P) 2 Pt(CO)Br [2,3] as a model, iron carbonyl thioboronyl derivatives might be accessible from the reaction of Me 3 SiSBBr 2 with low-valent iron carbonyl derivatives such as Na 2 Fe(CO) 4 or Fe 2 (CO) 9 followed by elimination of Me 3 SiBr. Reductive debromination of the anticipated Fe(CO) 4 (BS)Br product from this synthetic sequence could then provide a synthetic entry into binuclear iron carbonyl thioboronyl chemistry.…”

“…In view of the challenges in synthesizing metal complexes of BS, as well as the other diatomic boron ligands, theoretical studies are important to predict the potentially most productive areas of their coordination chemistry to explore using indirect synthetic methods. In this connection we used density functional theory to study the binuclear thioboronyl complex Fe 2 (BS) 2 (CO) 8 [6] analogous to the wellknown stable Mn 2 (CO) 10 [7,8] as well as the oxygen analogue Fe 2 (BO) 2 (CO) 8 , the subject of a previous theoretical study [9]. These previous studies suggest that Fe 2 (BS) 2 (CO) 8 is not a promising synthetic objective since its decomposition into Fe(CO) 5 + Fe 2 (BS) 2 (CO) 3 is exothermic.…”

A Tale of Two Stabilities: How One Boron Atom Affects a Switch in Bonding Motifs in CeO2Bx– (x = 2, 3) Complexes

“…With the ubiquity of carbon monoxide in organometallic compounds, integral in both catalysis and synthesis, there have been significant efforts to expand the breadth and specificity of their chemical reaches using isolobal and isoelectronic CO analogues. − Boronyl (BO – ) is one such example, ,, yet metal–(BO) n complexes have been largely elusive in non-gas-phase experiments, unlike other main group elements multiply bound to boron, for example, BN. , The highly polarized BO ligand acts as a strong nucleophile from the electron density localized on the O atom, with a tendency for cyclo-oligomerization with any nearby BO units. − Transition metals do stabilize small reactive functionalities like carbenes through electronic and steric effects, but only recently did Braunschweig and co-workers synthesize the first metal–BO complex, trans -[(Cy 3 P) 2 BrPtBO], in which the boronyl moiety is stabilized by a Pt­(II) center. This work inspired both experimentalists and theorists to explore several derivatives of trans -[(Cy 3 P) 2 BrPtBO] − as well as the potential stabilization of boronyls by other metals. ,− While some unexpected observations resulted, such as the synthesis of a trinuclear ruthenium complex capped with a BO unit, the general theme that has emerged is that an electron-rich metal center is necessary to stabilize the polar BO bond. And while B-centered polyboronyls have been previously observed and characterized in the gas phase, metal–boronyl complexes have yet to be observed with more than one boronyl ligand.…”