Coordination and Activation of the BF Molecule

Abstract

No CO: Fluoroborylene (BF), isoelectronic with CO and N(2), can be trapped by a transition metal. The structurally characterized complex [{CpRu(CO)(2)}(2)(mu-BF)] contains an unsupported bridging BF ligand, which is unprecedented in the structural chemistry of CO. With AlCl(3) , metal-bound CO coordinates through the O atom without bond rupture, while the more polar and less pi-bonded BF ligand is heterolytically cleaved (see picture).

Syntheses and Characterization of New Vinyl‐Borylene Complexes by the Hydroboration of Alkynes with [(μ3‐BH)(Cp*RuCO)2(μ‐CO)Fe(CO)3]

“…Ruthenium complexes of boron, which are characterized by two‐center, two‐electron bond between the ruthenium and boron, are exceptionally unusual. In particular, the isolated and structurally characterized ruthenium‐borylene complexes are still restricted to few examples, such as [RuHCl(BMes)(PCy 3 ) 2 ],13 [CpRu(CO) 2 {B(NCy 2 )}] + [BAr f 4 ] − ⋅ CH 2 Cl 2 ,18a [CpRu(dmpe)(BNMe 2 )]Cl18b [{CpRu(CO) 2 } 2 (μ‐BF)]19a and [CpRu(CO) 2 (BN i Pr 2 )] + [BAr f 4 ] −[19b] (Table 2). Herein, we report the first vinyl‐borylene complexes 2 – 4 , which are unparalleled in borylene chemistry.…”

Synthesis and structural characterization of terminal (diisopropylamino)borylene complexes of group 8 metals

“…The nature of the iron-boron interaction in 3 can be further compared to those found in the related cationic systems [Cp*Fe(CO) 2 (BMes)] + [10] and [CpFe(CO) 2 (BCp*)] + [12] for which Fe-B distances of 1.792(8) and 1.977(3) Å have been measured. The former compound has been described as containing significant Fe = B double bond character, the latter in terms of a simple B→Fe donor/acceptor interaction, with the differences between the two reflecting the π donor capabilities of the borylene substituents and their effects on the extent of Fe→B back-bonding.…”

“…Very recent additions to this family of compounds are transition metal complexes containing the simple Group 13 monohalides as ligands. These include structurally characterized complexes containing terminal GaI [8,9] or bridging BF [10] ligands which are valence isoelectronic with the widespread and chemically important molecules CO and N 2 .…”

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

“…Thus indirect methods are required to introduce the BX ligands into metal complexes. The first metal complex of a diatomic BX ligand to be synthesized and characterized structurally was the fluoroborylene (BF) complex (g 5 -C 5 H 5 ) 2 Ru 2 (CO) 4 (l-BF), reported in 2009 by Vidović and Aldridge [1]. Their synthesis replaced two of the three fluorine atoms in BF 3 with the strong nucleophile NaRu(CO) 2 (g 5 -C 5 H 5 ) thereby generating the BF ligand in the binuclear ruthenium complex.…”