Starting with electron-rich ditriflato-diborane B(hpp)(OTf) (hpp = 1,3,4,6,7,8-hexahydro-2-pyrimido[1,2-]pyrimidinate), novel symmetric and unsymmetric diboranes B(hpp)X and B(hpp)XY with X,Y = Br, NCS, N or OTf are synthesized by substitution reactions with S1 mechanisms. The stability of the unsymmetric diboranes with respect to dismutation equilibria is evaluated.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d1cc06359f | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Stereoselective Unsymmetrical 1,1-Diborylation of Alkynes with a Neutral sp -sp Diboron Reagent.
Angew Chem Int Ed Engl
November 2023
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong SAR, China.
The incorporation of two distinct boryl groups at the same carbon center in organic molecules has attracted growing research interest due to its potential for facilitating controlled, precise synthesis through stepwise dual carbon-boron bond transformations. Here we report a method to access unsymmetrical 1,1-diborylalkene (UDBA) stereoselectively via the reaction of readily available alkynes with a neutral sp -sp diboron reagent (NHC)BH -Bpin (NHC=N-heterocyclic carbene). Attributing to the chemically easily distinguishable nature of the sp and sp boryl moieties, controllable stepwise derivatization of the resultant UDBAs is realized.
View Article and Find Full Text PDFSynthesis, Reactivity and Coordination Chemistry of Group 9 PBP Boryl Pincer Complexes: [(PBP)M(PMe)] (M = Co, Rh, Ir; = 1, 2).
Molecules
August 2023
Institute of Inorganic and Analytical Chemistry, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
The unsymmetrical diborane(4) derivative [(d(CHP(Pr))abB)-Bpin] () proved to be a versatile PBP boryl pincer ligand precursor for Co(I) (, ), Rh(I) (-) and Ir(I/III) (-, -) complexes, in particular of the types [(d(CHP(Pr))abB)M(PMe)] (-) and [(d(CHP(Pr))abB)M-PMe] (-). Whilst similar complexes have been obtained before, for the first time, the coordination chemistry of a homologous series of PBP pincer complexes, in particular the interconversion of the five- and four-coordinate complexes -/-, was studied in detail. For Co, instead of the mono phosphine complex , the dinitrogen complex [(d(CHP(Pr))abB)Co(N)(PMe)] () is formed spontaneously upon PMe abstraction from in the presence of N.
View Article and Find Full Text PDFLigand properties of boryl ligands in bis-boryl rhodium(III) complexes: a case study.
Dalton Trans
March 2022
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
The oxidative addition of five diborane(4) derivatives, symmetrical and unsymmetrical, to [Rh(PMe)Cl] was studied. Only for the more electron poor diboron derivatives, Bcat, Bpin and catB-Bpin the resulting octahedral bis-boryl complexes [(PMe)Rh(boryl)Cl] were obtained, while for the more electron rich congeners only the equilibrium oxidative addition (catB-Bdmab) or no significant reaction (pinB-Bdmab) was observed (pin = (OCMe), cat = 1,2-OCH, dmab = 1,2-(NMe)CH). By abstraction of the chlorido ligand with NaBArF (BArF = tetrakis-[3,5-bis-(trifluormethyl)-phenyl]-borat) in the presence of a neutral ligand (L = PMe, MeCN, MeNC) the corresponding cationic octahedral complexes [(PMe)Rh(boryl)L] were obtained.
View Article and Find Full Text PDFDirected Synthesis and Chemistry of Unsymmetric Dicationic Diboranes and Their Use in Frustrated Lewis Pair-like Chemistry.
Chemistry
March 2022
Anorganisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
The chemistry of dicationic diboranes with two B atoms that are engaged in direct B-B bonding is by enlarge unexplored, although these molecules have intriguing properties due to their combined Lewis acidic and electron-donor properties. Unsymmetric dicationic diboranes are extremely rare, but especially attractive due to their polarized B-B bond. In this work we report the directed synthesis of several stable unsymmetric dicationic diboranes by reaction between the electron-rich ditriflato-diborane B (hpp) (OTf) (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate) and phosphino-pyridines, establishing B-N and B-P bonds with the diborane concomitant with triflate elimination.
View Article and Find Full Text PDFDerivatization of an especially electron-rich diborane.
Chem Commun (Camb)
January 2022
Inorganic Chemistry, Ruprecht-Karls-University Heidelberg Im Neuenheimer Feld 270, Heidelberg 69120, Germany.
Starting with electron-rich ditriflato-diborane B(hpp)(OTf) (hpp = 1,3,4,6,7,8-hexahydro-2-pyrimido[1,2-]pyrimidinate), novel symmetric and unsymmetric diboranes B(hpp)X and B(hpp)XY with X,Y = Br, NCS, N or OTf are synthesized by substitution reactions with S1 mechanisms. The stability of the unsymmetric diboranes with respect to dismutation equilibria is evaluated.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!