Expansion of the (BB)Ru metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls

Eleazer, Bennett J.; Smith, Mark D.; Popov, Alexey A.; Peryshkov, Dmitry V.

doi:10.1039/c8sc00190a

Cited by 34 publications

(15 citation statements)

References 119 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previously reported 2-B-metalated m -carborane complexes exhibit significantly larger values of the analogous B2–B1–M angle in the range from 104.5(1)° to 120(1)°, with the only exception being the ruthenium BB–carboryne complex previously synthesized in our group featuring two adjacent 2c-2e metal–boron bonds. 13 – 16 , 37 , 45 Thus, the presence of the strong B–H···Ru interaction in 2 led to the unprecedented distortion of the vicinal metal boryl bond. The coordination geometry of the ruthenium center is, therefore, octahedral, with the borane B–H bond serving as one of the ligands.…”

Section: Resultsmentioning

confidence: 99%

Rapid reversible borane to boryl hydride exchange by metal shuttling on the carborane cluster surface

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

Rapid reversible borane to boryl hydride exchange by metal shuttling on the carborane cluster surface

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…On the other hand, the reactivity of m -carborane is less studied but for the C c -H vertexes, which are less acidic as compared to the C c -H vertexes of the o -isomer [ 10 , 26 ]. Using a similar strategy as for o -carborane, a wide variety of 1-R-1,7- closo -C 2 B 10 H 11 and 1,7-R 2 -1,7- closo -C 2 B 10 H 10 derivatives has been developed [ 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ]. To some extent, the current state of knowledge of the m -carborane functionalization through the B-H vertexes is in an odd situation.…”

Section: Introductionmentioning

confidence: 99%

“…As compared to the o -carborane, a much-limited number of protocols leading to modify the B-H vertexes in the m -cluster have been reported [ 8 , 11 ]. In this context, very few derivatives of m -carborane with a functional group that is bonded to B(9) or B(9) and B(10) synchronously have been described [ 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ]. The Pd-catalyzed cross-coupling reaction of 9-X-1,7- closo -C 2 B 10 H 11 and 9,10-X 2 -1,7- closo -C 2 B 10 H 10 (X= halogen atom) represents one of these examples of derivatization [ 34 , 36 , 37 ].…”

Section: Introductionmentioning

confidence: 99%

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

et al. 2020

View full text Add to dashboard Cite

Closo m-C2B10H12 can perform as a novel core of globular periphery-decorated macromolecules. To do this, a new class of di and tetrabranched m-carborane derivatives has been synthesized by a judicious choice of the synthetic procedure, starting with 9,10-I2-1,7-closo-C2B10H10. The 2a-NPA (sum of the natural charges of the two bonded atoms) value for a bond, which is defined as the sum of the NPA charges of the two bonded atoms, matches the order of electrophilic reaction at the different cluster bonds of the icosahedral o-and m- carboranes that lead to the formation of B-I bonds. As for m-carborane, most of the 2a-NPA values of B-H vertexes are positive, and their functionalization is more challenging. The synthesis and full characterization of dibranched 9,10-R2-1,7-closo-carborane (R = CH2CHCH2, HO(CH2)3, Cl(CH2)3, TsO(CH2)3, C6H5COO(CH2)3, C6H5COO(CH2)3, N3(CH2)3, CH3CHCH, and C6H5C2N3(CH2)3) compounds as well as the tetrabranched 9,10-R2-1,7-R2-closo-C2B10H8 (R = CH2CHCH2, HO(CH2)3) are presented. The X-ray diffraction of 9,10-(HO(CH2)3)2-1,7-closo-C2B10H10 and 9,10-(CH3CHCH)2-1,7-closo-C2B10H10, as well as their Hirshfeld surface analysis and decomposed fingerprint plots, are described. These new reported tetrabranched m-carborane derivatives provide a sort of novel core for the synthesis of 3D radially grown periphery-decorated macromolecules that are different to the 2D radially grown core of the tetrabranched o-carborane framework.

show abstract

“…Among the presently available boron vertex functionalization methods, metal-catalyzed transformations enable the installation of the broadest class of chemical groups. These metal-catalyzed methods can be loosely grouped into (1) directed B–H activation and (2) cross-coupling at B–X bonds (X = Br, I). − While B–H activation methods often target the electron-deficient B–H vertices (those closest to the carbon vertices), , cross-coupling at B–X bonds can occur at electron-rich and electron-poor boron vertices . Thus, direct and selective synthesis of halocarborane regioisomers is the main challenge for synthesizing the corresponding regioisomeric carborane products via metal-catalyzed cross-coupling.…”

Section: Introductionmentioning

confidence: 99%

Off-Cycle Processes in Pd-Catalyzed Cross-Coupling of Carboranes

Dziedzic

Axtell

Rheingold

et al. 2019

Org. Process Res. Dev.

View full text Add to dashboard Cite

Off-cycle processes in a catalytic reaction can dramatically influence the outcome of the chemical transformation and affect its yield, selectivity, rate, and product distribution. While the generation of off-cycle intermediates can complicate reaction coordinate analyses or hamper catalytic efficiency, the generation of such species may also open new routes to unique chemical products. We recently reported the Pd-mediated functionalization of carboranes with a range of ON N-, and C-based nucleophiles. By utilizing a Pd-based catalytic system supported by a biarylphosphine ligand developed by Buchwald and coworkers, we discovered an off-cycle isomerization process ("cage-walking") that generates four regioisomeric products from a single halogenated boron cluster isomer. Here we describe how several off-cycle processes affect the regioisomer yield and distribution during Pd-catalyzed tandem cage-walking/cross-coupling. In particular, tuning the transmetalation step in the catalytic cycle allowed us to incorporate the cage-walking process into Pd-catalyzed cross-coupling of sterically unencumbered substrates, including cyanide. This work demonstrates the feasibility of using tandem cage-walking/cross-coupling as a unique low-temperature method for producing regioisomers of monosubstituted carboranes.

show abstract

Expansion of the (BB)Ru metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls

Abstract: Assembly of bimetallic complexes on boron clusters by coordination of coinage metal cations to Ru–B single bonds.

Cited by 34 publications

References 119 publications

Rapid reversible borane to boryl hydride exchange by metal shuttling on the carborane cluster surface

Rapid reversible borane to boryl hydride exchange by metal shuttling on the carborane cluster surface

m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

Off-Cycle Processes in Pd-Catalyzed Cross-Coupling of Carboranes

Contact Info

Product

Resources

About