Oxygenation of a Ruthenium Complex Bearing a PBP-Pincer Ligand Inducing the Formation of a Boronato Ligand with a Weak Ru–O Bond

Miyada, Takuma; Yamashita, Makoto

doi:10.1021/om400915x

Cited by 61 publications

(25 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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. This not 55 only supports the intramolecular evolution of H 2 S but also suggests that the insertion of S in the B-H bond of LB(SH)H to be more facile than that in LBH 2 itself with concomitant release of H 2 S from 3. In this respect, the behaviour of Se analogue 4 was found to be similar to that of 3.…”

Section: Resultssupporting

confidence: 55%

“…4 Frontier Kohn-Sham orbitals on B=S unit of compound 3. 55 The three KS occupied π orbitals shown in Fig. 5 are mainly nitrogen centered with almost no contribution from phosphorus atoms.…”

Section: Resultsmentioning

confidence: 96%

“…20 The 11 B NMR spectrum of 2 showed a sharp doublet at 3.30 ppm with 1 J B-H of 164.3 Hz, this signal can be attributed to the anionic moiety of 2. 28 The signal 55 for B atom of the cationic moiety is not detected perhaps due to the low local symmetry around this boron atom. Single crystals of 2 suitable for X-ray structural analysis were 70 grown from toluene.…”

Section: Resultsmentioning

confidence: 99%

“…The lack of a suitable starting material and a rational synthetic route are major synthetic challenges in this area. The alkyl or aryl borinic (R 2 BOH) and boronic (RB(OH) 2 ) acids 11 are easily prepared and have been used extensively in organic synthesis as 55 building blocks and as intermediates in Suzuki coupling. 12 Additionally, the dihydroxyborenium cation [NHC-B(OH) 2 ] + TfO − is also known.…”

Section: Introductionmentioning

confidence: 99%

See 3 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

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 55%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

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

View full text Add to dashboard Cite

show abstract

“…In the presence of CO, 57 exists in equilibrium with (PBP)Ru(Cl)(CO) 2 (58 The alkylphosphino-PBP precursor 1a could also be used for the formation of (PBP)Ru complexes (Scheme 21). 71 Reaction of 1a with [Ru(CO) 3 (cod)] afforded (PBP)Ru(H)(CO) 2 (62) via an oxidative addition of the BH bond. Monoxygenation of 62 was achieved with N-methylmorpholine N-oxide (NMO), furnishing oxygen-inserted hexacoordinate complex 63.…”

Section: Group 10 Metalmentioning

confidence: 99%

The Organometallic Chemistry of Boron-Containing Pincer Ligands based on Diazaboroles and Carboranes

Yamashita

2015

Bulletin of the Chemical Society of Japan

Self Cite

View full text Add to dashboard Cite

In this article, recent developments regarding the organometallic chemistry of boron-containing pincer ligands are reviewed. Boron-based pincer ligands can be subdivided into two main classes, which are based on either diazaborole or carborane. All the papers relevant to such boron-based pincer ligands that have been published since 2009 are included in this review, which also summarizes applications of transition-metal complexes containing such boron-containing pincer ligands in catalytic and/or bond-cleavage reactions.

show abstract

The Chemistry of Multibonded Organoboron Compounds

Devillard

Alcaraz

2020

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

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.

show abstract

Oxygenation of a Ruthenium Complex Bearing a PBP-Pincer Ligand Inducing the Formation of a Boronato Ligand with a Weak Ru–O Bond

Cited by 61 publications

References 43 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

The Organometallic Chemistry of Boron-Containing Pincer Ligands based on Diazaboroles and Carboranes

The Chemistry of Multibonded Organoboron Compounds

Contact Info

Product

Resources

About