Reactions of [Cp*RuCl]4 and [(p-cymene)RuCl2]2 with the Tridentate Ligand [Ph(pz)B(μ-O)(μ-pz)B(pz)Ph]−

Mutseneck, Elena V.; Reus, Christian; Schödel, Frauke; Bolte, Michael; Lerner, Hans‐Wolfram

doi:10.1021/om901022d

Cited by 14 publications

(15 citation statements)

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“…A similar, however less pronounced trend is also observed for the B2–O2 (1.389(2) Å) and B2–O3 (1.368(2) Å) distances. Furthermore, the B1–O2/O4 and B2–O2/O3 distances are within the normal range of four‐ (1.463(4)–1.479(6) Å), and three‐coordinate (1.352(3)–1.368(2) Å), boronic acid derivatives respectively. Also the B1–N2 (1.582(2) Å), B1–C12 (1.584(3) Å), and the B2–C6 (1.540(3) Å) atomic distances are all in the typical range for boronic acid derivatives with four‐ and three‐coordinate boron atoms respectively.…”

Section: Resultsmentioning

confidence: 80%

Synthesis of a Boronic Acid Anhydride Based Ligand and Its Application in Beryllium Coordination

et al. 2019

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The synthesis of a boronic acid anhydride‐based ligand containing one three‐ and one four‐coordinated boron atom is presented. This ligand was successfully employed as a tridentate κ1N,κ2O‐ligand in the coordination of beryllium chloride and both the ligand and the resulting complex have been structurally characterized. While the boron‐element separations are within the typical range of related homo‐nuclear compounds, the corresponding beryllium‐element distances are rather long, suggesting unexpectedly high electron density at the beryllium center. Incorporation of a beryllium atom in a six‐membered ring causes no more distortion than the corresponding boron atom, suggesting that analogous ligand systems could be used in boron and beryllium coordination chemistry. The generated hetero‐tri‐nuclear complex enables the direct comparison of bond lengths and angles at beryllium and boron atoms in similar coordination environments and can act as a monomolecular model for beryllium borates.

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Section: Resultsmentioning

confidence: 80%

Synthesis of a Boronic Acid Anhydride Based Ligand and Its Application in Beryllium Coordination

et al. 2019

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“…Furthermore, slight shortening (0.03 Å) of the neighboring Si(1)–O(3) and B(2)–O(5) bonds was observed. The N(1)–B(1) bond distance is 1.681(2) Å, which is slightly longer than in the monoadducts of boroxines (ArBO) 3 L, where L is an aliphatic or aromatic N-donor ligand (1.61 to 1.67 Å). − Surprisingly, this boron nitrogen interaction does not affect the planarity of the B 2 O 3 Si ring, and in fact, the values for the SiOBO torsion angles decreased from 11.3° and 13.1° ( 1 ) to 1.5° and 12.3° ( 6 ). Additionally, the N–H protons are involved in a N–H···π intramolecular interaction with one of the Ph rings of the Ph 3 CO group, where the H···centroid distance is 2.719 Å, and the N–H···centroid angle is nearly linear (178.8°; Table ).…”

Section: Resultsmentioning

confidence: 96%

Synthesis of Cyclic and Cage Borosilicates Based on Boronic Acids and Acetoxysilylalkoxides. Experimental and Computational Studies of the Stability Difference of Six- and Eight-Membered Rings

et al. 2017

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A series of borosilicates was synthesized, where the structure of the borosilicate core was easily modulated using two strategies: blocking of condensation sites and controlling the stoichiometry of the reaction. Thus, on the one hand, the condensation of phenylboronic or 3-hydroxyphenylboronic acid with diacetoxysilylalkoxide [(BuO)(PhCO)Si(OAc)] led to the formation of borosilicates (BuO)(PhCO)Si{(μ-O)BPh}(μ-O) (1), [{(BuO)(PhCO)Si(μ-O)BPh(μ-O)}] (2), and [{(BuO)(PhCO)Si(μ-O)B(3-HOPh)(μ-O)}] (3) with a cyclic inorganic BSiO or BSiO core, respectively. On the other hand, the reaction of phenylboronic acid with triacetoxysilylalkoxide (PhCO)Si(OAc) in 3:2 ratio resulted in the formation of a cagelike structure [{(PhCO)Si(μ-O)BPh(μ-O)}] (4) with BSiO core, while the reaction of the boronic acid with silicon tetraacetate generated an unusual 1,3-bis(acetate)-1,3-diphenyldiboraxane PhB(μ-O)(μ-O,O'-OAc)BPh (5). Additionally, compound 1 was used to evaluate the possibility to form N→B donor-acceptor bond between the boron atom in the borosilicates and a nitrogen donor. Thus, coordination of 1 with piperazine yielded a tricyclic [{(BuO)(PhCO)Si(OBPh)(μ-O)}·CHN] compound 6 with two borosilicate rings bridged by a piperazine molecule. Finally, the processes involved in the formation of the six- and eight-membered rings (BSiO and BSiO) in compounds 1 and 2 were explored using solution H NMR studies and density functional theory calculations. These molecules represent to the best of our knowledge first examples of cyclic molecular borosilicates containing SiO units.

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“…The N→B bond distances in 1a·THF (1.702 and 1.707 Å) are practically identical to those in 1a·Acetone (1.694 and 1.699 Å). For comparison, N→B bond distances for monoadducts (ArBO) 3 L and 1:2 adducts (PhBO) 3 ·2L with Ar = aryl and L = aliphatic or aromatic N-donor ligand have values in the range of 1.61–1.67 Å and 1.64–1.74 Å, respectively. − ,− , The coordination geometry around the sp 3 boron atoms in 1a·THF and 1a·Acetone corresponds to a distorted tetrahedron with bond angles in the range of 101.3–115.7°. The third noncoordinated boron atom has a trigonal-planar geometry with angles between 117.6° and 122.9°.…”

Section: Resultsmentioning

confidence: 99%

“…For comparison, N→B bond distances for monoadducts (ArBO) 3 L and 1:2 adducts (PhBO) 3 •2L with Ar = aryl and L = aliphatic or aromatic N-donor ligand have values in the range of 1.61−1.67 Å and 1.64−1.74 Å, respectively. [65][66][67][68][69][70][71][72][73][79][80][81][82][83]91 The coordination geometry around the sp 3 The propagation of neighboring chains in compounds 1a• THF and 1a•Acetone generates pseudocavities, which are filled by the corresponding solvent (Figure 2). In both cases, the oxygen atom of the solvent is involved in the formation of asymmetric 4c).…”

Section: Preparation and Spectroscopic Characterizationmentioning

confidence: 99%

“…Derivatives of boronic acids have been widely used as building blocks in the development of ordered structures to generate macrocycles, cages, calixarene systems, or two- and three-dimensional networks. − Boroxines are anhydrides of organoboronic acids and contain a heterocyclic B 3 O 3 ring and have been also successfully applied as building blocks for macrocycles, molecular cages, polymers, and three-dimensional networks, − with applications in methane storage, electronic , and optical devices, and as a source of aryl and vinyl groups. , Additionally, they can easily form supramolecular systems due to their ability to generate N→B coordinative bonds with organic amines . Although the boroxine B 3 O 3 ring is theoretically capable of coordinating up to three nitrogen atoms, it is well-known that the most stable adducts involve the interaction with only one nitrogen atom per ring, − as reflected in the number of structures reported with this stoichiometric composition. − In contrast, triarylboroxine species carrying aryl rings with amine substituents in the ortho position represent the few examples, in which a B 3 O 3 ring is coordinated to more than one nitrogen atom. − The number of 1:2 boroxine/amine adducts is limited and 1:3 adducts with independent organic amines are currently unknown. − With the interest in organoboron compounds and their applications in supramolecular chemistry taken into account, the study of the susceptibility of these assemblies toward the properties of the solvent is relevant, mainly because the lability of the N→B bond in the corresponding adducts is well-known …”

Section: Introductionmentioning

confidence: 99%

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Structural Induction via Solvent Variation in Assemblies of Triphenylboroxine and Piperazine—Potential Application as Self-Assembly Molecular Sponge

Torres-Huerta

Velásquez‐Hernández

Martı́nez-Otero

et al. 2017

Crystal Growth & Design

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This study examined the direct effect of solvent on the chemical composition and structure of supramolecular assemblies formed from triphenylboroxine ((PhBO) 3 ) and piperazine (ppz) through N→B bonds. Oxygen-containing solvents with a molecular size smaller than 4.1 Å produce 1D polymeric structures (1:1 boroxine/piperazine) of compositions {(PhBO) 3 (ppz)} n •nTHF (1a• THF) and {(PhBO) 3 (ppz)} n •nAcetone (1a•Acetone), in which the boroxine B 3 O 3 rings are linked through N→B bonded piperazine molecules in a cis-conformation. In both cases, a pseudocavity is generated between two polymer chains, which is occupied by a solvent molecule interacting through bifurcated N−Hbonds with one of the chains. In contrast, oxygen-based solvents with a size larger than 6.3 Å give rise to discrete 2:1 assemblies, {(PhBO) 3 } 2 (ppz)•2Ethyl acetate (2•AcOEt) and {(PhBO) 3 } 2 (ppz)•2Pentanone (2•Pentanone), with the piperazine molecule bridging two B 3 O 3 rings and interacting with two solvent molecules via N−H•••O hydrogen bonds. In chloroform or dichloromethane 2:3 adducts, {(PhBO) 3 } 2 (ppz) 3 •4CHCl 3 (3•CHCl 3 ) and {(PhBO) 3 } 2 (ppz) 3 •2.09CH 2 Cl 2 (3•CH 2 Cl 2 ), were obtained, with N−H•••N interactions formed between the piperazine molecules directing the crystal lattice. Finally, unlike with THF and acetone, the presence of two coordination sites in dioxane gives rise to a 1D polymeric 1:1 clathrate-type assembly with trans-conformation, {(PhBO) 3 (ppz)} n •3.5nDioxane (1b•Dioxane). In accordance with the structural characterization, the thermogravimetric analysis of compounds 1−2 evidenced relatively high decomposition (solvent elimination) temperatures for the inclusion complexes derived from oxygen-containing solvents (T peak = 76.4 to 145.4 °C). On the contrary, solvates based on halogenated solvents (3•CHCl 3 and 3•CH 2 Cl 2 ) or 1,4-dioxane started to decompose already at room temperature. In view of potential applications for the storage and structural characterization of volatile or highly reactive reagents, a final inclusion experiment was carried out with racemic 1,2-epoxybutane. As expected, the resulting N→B bonded inclusion complex exhibited a 1:1 cis-polymeric structure, in which the guest molecules were bonded by bifurcated N pip −H•••O epoxy •••H−N pip hydrogen bonds.

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Reactions of [Cp*RuCl]₄ and [(p-cymene)RuCl₂]₂ with the Tridentate Ligand [Ph(pz)B(μ-O)(μ-pz)B(pz)Ph]⁻

Cited by 14 publications

References 84 publications

Synthesis of a Boronic Acid Anhydride Based Ligand and Its Application in Beryllium Coordination

Synthesis of a Boronic Acid Anhydride Based Ligand and Its Application in Beryllium Coordination

Synthesis of Cyclic and Cage Borosilicates Based on Boronic Acids and Acetoxysilylalkoxides. Experimental and Computational Studies of the Stability Difference of Six- and Eight-Membered Rings

Structural Induction via Solvent Variation in Assemblies of Triphenylboroxine and Piperazine—Potential Application as Self-Assembly Molecular Sponge

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