Isolation of a Three‐Coordinate Boron Cation with a Boron–Sulfur Double Bond

Franz, Daniel; Irran, Elisabeth; Inoue, Shigeyoshi

doi:10.1002/anie.201407809

Cited by 70 publications

(58 citation statements)

References 74 publications

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“…20 The 11 B NMR spectrum of 3 (and 4) 45 revealed a broad resonance at 41 ppm (and 45.2 ppm), suggesting a low local symmetry around the boron atom for three coordinated boron species. 9,10 This also excludes the possibility of any dimer formation (B 2 S 2 core), due to [2+2] addition of the B=S bonds in the solution state. To rule out any H 2 evolution 50 from the possible intermediate LB(SH)H species, leading to 3, we performed a stoichiometric reaction between LBH 2 and S. To our surprise, as monitored by in-situ 31 P{ 1 H} NMR measurements, almost half of the starting material was consumed to form only 3 and the remaining half of LBH 2 was present unreacted.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction of sulfur with compound 2 did not progress at room temperature however, under reflux conditions in 5 toluene the insertion of sulfur presumably occurs converting the hydride into a thiol function which due to the presence of HBCl 3 anion releases HCl and formation of [LH 2 ] + Clas the only isolable soluble product. Use of Et 3 N or lutidine as bases in the reaction lead to the isolation of the mixture of ammonium salts 10 and [LH 2 ] + Cl -.…”

Section: Resultsmentioning

confidence: 99%

“…10 35 The corresponding Se analogue has not been reported as yet. Therefore, we believe that synthesis and characterization of stable 45 For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b000000x/ molecules of boron containing thiol & selenol functionality and boron doubly bonded with S and Se is an important step towards rationalization of electronic structure, bonding, and chemical 50 reactivity of this class of compounds. The lack of a suitable starting material and a rational synthetic route are major synthetic challenges in this area.…”

Section: Introductionmentioning

confidence: 99%

“…We attempted oxidative insertion of elemental S (and Se) into the B-H bonds of compound 1 to explore the possibility of isolating a dithiol (and diselenol) and 5 the addition of sulfur into the B-H bond of compound 2 to prepare a cationic mercaptoborane. Our efforts rewarded us with the discovery of a facile synthesis of doubly bonded terminal LB=S (3) and LB=Se (4) compounds under H 2 S or H 2 Se evolution from the corresponding dithiol or diselenol 10 intermediate. However, reaction of compound 2 with sulfur leads to HCl evolution and formation of [LH 2 ] + Cl − as the only isolable product.…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of a dihydroboron species: synthesis of a hydroborenium complex and an expedient entry into stable thioxo- and selenoxo-boranes

et al. 2015

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The reaction of a recently synthesized dihydroboron species complexed with bis(phosphinimino)amide, LBH2 (), (L = [N(Ph2PN(2,4,6-Me3C6H2))2](-)) with 3 equivalents of BH2Cl·SMe2 or one equivalent of BCl3 affords the first stable monohydridoborenium ion, [LBH](+)[HBCl3](-) () that is stable without a weakly coordinating bulky anion. Compound can also be prepared directly by refluxing LH with 3 equivalents of BH2Cl·SMe2. Interestingly, reaction of LBH2 () with elemental sulfur and selenium involves oxidative addition of S and Se into B-H bonds and subsequent release of H2S (or H2Se) from the intermediate LB(SH)2 (or LB(SeH)2) species forming stable compounds with terminal boron-chalcogen double bonds LB[double bond, length as m-dash]S () and LB[double bond, length as m-dash]Se (). The electronic structures of compounds , and were elucidated by high resolution mass spectrometry, multi-nuclear NMR and single crystal X-ray diffraction studies. Ab initio calculations on are in excellent agreement with its experimental structure and clearly support the existence of the boron-sulfur double bond.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reactivity of a dihydroboron species: synthesis of a hydroborenium complex and an expedient entry into stable thioxo- and selenoxo-boranes

et al. 2015

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“…[1b] This tendency towards aggregation is problematic for applications which involve low-coordinate metal centres,f or example ambiphilic main-group species (such as carbenes and their heavier group 14 analogues) of interest in smallmolecule activation chemistry. [5] This attribute,i nc ombination with al arge steric profile has been exploited in the stabilization of lowcoordinate main-group systems, [6] including an acyclics ilanone. Thus,m onomeric species of the type (ArO) 2 E( E= Ge,S n, Pb) have been reported by Lappert and by Power using this approach.…”

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confidence: 99%

An N‐Heterocyclic Boryloxy Ligand Isoelectronic with N‐Heterocyclic Imines: Access to an Acyclic Dioxysilylene and its Heavier Congeners

et al. 2019

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Introduced here is an ew type of strongly donating N-heterocyclic boryloxy (NHBO) ligand, [(HCDippN) 2 BO] À (Dipp = 2,6-diisopropylphenyl), which is isoelectronic with the well-known N-heterocyclic iminato (NHI) donor class.T his 1,3,2-diazaborole functionalized oxyl igand has been used to stabilizet he first acyclic two-coordinate dioxysilylene and its Ge,Sn, and Pb congeners,thereby presenting the first complete series of heavier group 14 dioxycarbene analogues.A ll four compounds have been characterized by X-raycrystallography and density-functional theory,e nabling analysis of periodic trends:t he potential for the [(HCDippN) 2 BO] À ligand to subtly vary its electronic-donor capabilities is revealed by snapshots showing the gradual evolution of arene p coordination on going from Si to Pb.Anionic oxygen-based ligands constitute af amily of donors prevalent in the coordination chemistry of harder metal centers. [1] Among the most common are alkoxy (RO À ) ligands,w hich stand out in having only one pendant substituent, thereby giving them the potential to donate 2s + 4p electrons to ametal center-the maximum for any h 1 ligand system. Thes ingle substituent, however, offers only limited steric protection at the metal center, meaning that Obridged oligomeric structures are commonly encountered. [1b] This tendency towards aggregation is problematic for applications which involve low-coordinate metal centres,f or example ambiphilic main-group species (such as carbenes and their heavier group 14 analogues) of interest in smallmolecule activation chemistry. [2] An approach used to counter this problem exploits aryloxy (ArO À )l igands featuring bulky ortho substituents, thereby extending steric protection towards the metal center. Thus,m onomeric species of the type (ArO) 2 E( E= Ge,S n, Pb) have been reported by Lappert and by Power using this approach. [1c-e] That said, further chemistry with these systems typically involves the ArO À unit acting as aleaving group (cf. pK a of phenol % 9), and being substituted by as tronger donor. [1f] Apotential strategy to circumvent this problem is to replace the O-bound aryl substituent with afunctional group based on amore electro-positive element such as boron (e.g., by employing boryloxy ligands,R 2 BO À ). As mall number of ligands of this type have been reported, although for R = alkyl or aryl these are typically considered as electron-deficient alkoxide variants:t he formally empty p-orbital at boron renders the R 2 BO À system aweak p donor. [3] Applications in main-group chemistry are thus rare (limited primarily to groups 1, 2a nd 13 complexes), [3b-d] although very recently Sarazin and co-workers isolated monomeric species of the type (R 2 BO) 2 E( E = Sn, Pb,B a) by employing the bulky (Me 3 Si) 2 HC group to inhibit dimerization. [3e-f] With aview to targeting an isolable dioxysilylene,wesaw an eed for more strongly p-donating boryloxy ligands which would potentially lead to awide HOMO-LUMO gap on the basis of LUMO destabilization (O-to-Si p donation) and...

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The Chemistry of Multibonded Organoboron Compounds

Devillard

Alcaraz

2020

Patai's Chemistry of Functional Groups

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Multiply bonded boron species are fascinating objects of study addressing concerns about the chemical bonding. Although mostly exemplified with light p‐block elements, the use of Group 6–10 transition metals as models to more clearly understand and rationalize the bonding in this family of compounds has also proved successful. In this prospect, the interplay between experiment and theory pushes forward the frontiers of the analysis based on the metric parameters, and it clearly appears that the notion of doubly or triply bonded boron in such species must be qualified. The bond orders are more often partial involving more or less polarized bonds responsible for the chemical reactivity. These features are developed in this chapter starting with the nearest neighbors of boron and finishing with the case of transition metals.

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Isolation of a Three‐Coordinate Boron Cation with a Boron–Sulfur Double Bond

Cited by 70 publications

References 74 publications

Reactivity of a dihydroboron species: synthesis of a hydroborenium complex and an expedient entry into stable thioxo- and selenoxo-boranes

Reactivity of a dihydroboron species: synthesis of a hydroborenium complex and an expedient entry into stable thioxo- and selenoxo-boranes

An N‐Heterocyclic Boryloxy Ligand Isoelectronic with N‐Heterocyclic Imines: Access to an Acyclic Dioxysilylene and its Heavier Congeners

The Chemistry of Multibonded Organoboron Compounds

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