Synthesis and Hydroboration of a Mixed‐Donor Iminoboryl Complex of Platinum

Brand, Johannes; Braunschweig, Holger; Dewhurst, Rian D.; Hupp, Florian; Lang, Katharina

doi:10.1002/ejic.201500215

Cited by 10 publications

(3 citation statements)

References 30 publications

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“…X-ray diffraction studies of 4 shown in Figure b confirm its iminoborane connectivity with a nearly linear geometry of the B–B–N–B core [B1–B3–N5 angle = 176.7(8) o and B2–N5–B3 = 178.1(6) o ], demonstrating the formal sp-hybridized B3 and N5 atoms. The B3–N5 distance of 1.240(7) Å is shorter than those for structurally characterized Lewis-base-supported iminoboranes [1.300–1.360(5) Å] and comparable to the BN triple bond distances (about 1.25 Å) in typical base-free iminoborane species, − which suggests considerable multiple bond character between the central boron and nitrogen atoms.…”

Section: Resultsmentioning

confidence: 81%

“…However, with the help of sterically bulky organyls on either side of the BN triple bond, a variety of monomeric iminoboranes IV have been isolated and structurally characterized (Chart c) . In addition, the group of Braunschweig reported the isolation of transition-metal iminoboryl complexes V , which are stable against oligomerization, yet reactive toward various substrates . In 2014, Bertrand, Stephan, and co-workers found that reactions of a cyclic (alkyl)(amino)carbene (CAAC) with bis(trimethylsilyl)dihaloboranes afford cationic iminoboryl-CAAC adducts VI .…”

Section: Introductionmentioning

confidence: 99%

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Acid/Base-Free Acyclic Anionic Oxoborane and Iminoborane Bearing Diboryl Groups

et al. 2022

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Anionic oxoboranes and neutral iminoboranes, which are isoelectronic to ketones and alkynes, respectively, have attracted much attention because of their unique structures and various reactivity. However, acid/base-free oxoboranes and iminoboranes are still limited, and readily accessible examples with diverse electronic and steric characteristics are highly desirable. Herein, we report the first syntheses of the acyclic anionic oxoborane 2 and iminoborane 4 bearing two boryl ligands, both of which are acid/base-free. Spectroscopic analysis, X-ray crystallography, and theoretical calculations reveal that 2 and 4 possess a polarized terminal B�O double bond and central B�N triple bond, respectively.

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Section: Resultsmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Acid/Base-Free Acyclic Anionic Oxoborane and Iminoborane Bearing Diboryl Groups

et al. 2022

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“…Multimetallic transition-metal complexes containing a boron ligand have been synthesized by halide abstraction from boron, reduction of B–X bonds, and nucleophilic attack at a metal center at boron. − Also, iminoboryl (BNR , ) and oxoboryl (BO , ) complexes have been synthesized and reported. Computational − and experimental − studies have been reported for transition-metal boryl complexes (L n M–BR 2 ). Successful experimental attempts to synthesize terminal borylene (L n M(BR)) complexes ,− motivated us to model hypothetical terminal boride complexes.…”

Section: Introductionmentioning

confidence: 99%

Computational Analysis of Transition Metal-Terminal Boride Complexes

Ceylan¹,

Cundari

2017

J. Phys. Chem. A

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A computational analysis of model transition-metal terminal boride [MB(PNP)] complexes is reported. A combination of density functional theory methods, natural bond orbital analysis, and multiconfiguration self-consistent field calculations were employed to investigate the structure and bonding of terminal boride complexes, in particular, the extent of metal dπ-boron pπ bonding. Comparison of metal-boride, -borylene, and-boryl bond lengths confirms the presence of metal-boron π bonds, albeit the modest shortening (∼3%) of the metal-boron bond suggests that the π-bonding is very weak in terminal borides. Calculated free energies of H addition to the boride complexes to yield the corresponding boryl complexes indicate that metal-boride π-bond strengths are 22 kcal/mol or less as compared to 44 kcal/mol for an analogous nitride complex. It is concluded that, for the boride complexes studied, covering a range of different 4d and 5d metals, that the metal-boride bond consists of a reasonably covalent σ but two very polarized metal-boron π bonds. The high polarization of the boron-to-metal π bonds indicates that the terminal boride is an acceptor or Z-type ligand.

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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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Synthesis and Hydroboration of a Mixed‐Donor Iminoboryl Complex of Platinum

Cited by 10 publications

References 30 publications

Acid/Base-Free Acyclic Anionic Oxoborane and Iminoborane Bearing Diboryl Groups

Acid/Base-Free Acyclic Anionic Oxoborane and Iminoborane Bearing Diboryl Groups

Computational Analysis of Transition Metal-Terminal Boride Complexes

The Chemistry of Multibonded Organoboron Compounds

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