Isolable phosphanylidene phosphorane with a sterically accessible two-coordinate phosphorus atom.
Ontology highlight
ABSTRACT:
SUBMITTER: Surgenor BA
PROVIDER: S-EPMC3625738 | biostudies-literature | 2012 Oct
REPOSITORIES: biostudies-literature
Publications
Isolable phosphanylidene phosphorane with a sterically accessible two-coordinate phosphorus atom.
Surgenor Brian A BA Bühl Michael M Slawin Alexandra M Z AM Woollins J Derek JD Kilian Petr P
Angewandte Chemie (International ed. in English) 20120905 40
Similar Datasets
Project description:A rare three-coordinate germanone [IPrN]2 Ge=O (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-imino) was successfully isolated. The germanone has a rather high thermal stability in arene solvent, and no detectable change was observed at 80 °C for at least one week. However, high thermal stability of [IPrN]2 Ge=O does not prevent its reactivity toward small molecules. Structural analysis and initial reactivity studies revealed the highly polarized nature of the terminal Ge=O bond. Besides, the addition of phenylacetylene, as well as O-atom transfer with 2,6-dimethylphenyl isocyanide make it a mimic of nucleophilic transition-metal oxides. Mechanism for O-atom transfer reaction was investigated via DFT calculations, which revealed that the reaction proceeds via a [2+2] cycloaddition intermediate.
| S-EPMC9292218 | biostudies-literature
Project description:IPr* (IPr* = 1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) has emerged as a powerful highly hindered and sterically-flexible ligand platform for transition-metal catalysis. CAACs (CAAC = cyclic (al-kyl)(amino)carbenes) have gained major attention as strongly electron-rich carbon analogues of NHCs (NHC = N-heterocyclic carbene) with broad applications in both industry and academia. Herein, we report a merger of CAAC ligands with highly-hindered IPr*. The efficient synthesis, electronic characterization and application in model Cu-catalyzed hydroboration of alkynes is described. The ligands are strongly electron-rich, bulky and flexible around the N-Ar wingtip. The availability of various IPr* and CAAC templates offers a significant potential to expand the existing arsenal of NHC ligands to electron-rich bulky architectures with critical applications in metal stabilization and catalysis.
| S-EPMC9737351 | biostudies-literature
Project description:The monoatomic zero-valent tin complex (stannylone) {[SiII (Xant)SiII ]Sn0 } 5 stabilized by a bis(silylene)xanthene ligand, [SiII (Xant)SiII =PhC(NtBu)2 Si(Xant)Si(NtBu)2 CPh], and its bis-tetracarbonyliron complex {[SiII (Xant)SiII ]Sn0 [Fe(CO)4 ]2 } 4 are reported. The stannylone 5 bearing a two-coordinate zero-valent tin atom is synthesized by reduction of the precursor 4 with potassium graphite. Compound 4 results from the SnII halide precursor {[SiII (Xant)SiII ]SnII Cl}Cl 2 or {[SiII (Xant)SiII ]SnBr2 } 3 through reductive salt-metathesis reaction with K2 Fe(CO)4 . According to density functional theory (DFT) calculations, the highest occupied molecular orbital (HOMO) and HOMO-1 of 5 correspond to a π-type lone pair with delocalization into both adjacent vacant orbitals of the SiII atoms and a σ-type lone pair at the Sn0 center, respectively, indicating genuine stannylone character.
| S-EPMC9300062 | biostudies-literature
Project description:Besides its mathematical importance, the Möbius topology (twisted, single-sided strip) is intriguing at the molecular level, as it features structural elegance and distinct properties; however, it carries synthetic challenges. Although some Möbius-type molecules have been isolated by synthetic chemists accompanied by extensive computational studies, the design, preparation, and characterization of stable Möbius-conjugated molecules remain a nontrivial task to date, let alone that of molecular Möbius strips assembling into more complex topologies. Here we report the efficient synthesis, crystal structure, and theoretical study of a catenane consisting of two fully conjugated nanohoops exhibiting Möbius topology in the solid state. This work highlights that oligoparaphenylene-derived nanohoops, a family of highly warped and synthetically challenging conjugated macrocycles, can not only serve as building blocks for interlocked supermolecular structures, but also represent a new class of compounds with isolable Möbius conformations stabilized by non-covalent interactions.
| S-EPMC6072741 | biostudies-literature
Project description:The influence of substituents on α-borylated phosphorus ylides (α-BCPs) has been investigated in a combined experimental and quantum chemical approach. The synthesis and characterization of Me3 PC(H)B(iBu)2 (1), consisting of small Me substituents on phosphorous and iBu residues on boron, is reported. Compound 1 is accessible through a novel synthetic approach, which has been further elucidated through DFT studies. The reactivity of 1 towards various small molecules was probed and compared with that of a previously published derivative, Ph3 PC(Me)BEt2 (2). Both α-BCPs react with NH3 to undergo heterolytic N-H bond cleavage. Different di- and trimeric ring structures were observed in the reaction products of 1 with CO and CO2 . With PhNCO and PHNCS, the expected insertion products [Me3 PC(H)(PhNCO)B(iBu)2 ] and [Me3 PC(H)(PhNCS)B(iBu)2 ], respectively, were isolated.
| S-EPMC6771871 | biostudies-literature
Project description:A low-spin and mononuclear vanadium complex, (Me nacnac)V(CO)(η2 -P≡Ct Bu) (2) (Me nacnac- =[ArNC(CH3 )]2 CH, Ar=2,6-i Pr2 C6 H3 ), was prepared upon treatment of the vanadium neopentylidyne complex (Me nacnac)V≡Ct Bu(OTf) (1) with Na(OCP)(diox)2.5 (diox=1,4-dioxane), while the isoelectronic ate-complex [Na(15-crown-5)]{([ArNC(CH2 )]CH[C(CH3 )NAr])V(CO)(η2 -P≡Ct Bu)} (4), was obtained via the reaction of Na(OCP)(diox)2.5 and ([ArNC(CH2 )]CH[C(CH3 )NAr])V≡Ct Bu(OEt2 ) (3) in the presence of crown-ether. Computational studies suggest that the P-atom transfer proceeds by [2+2]-cycloaddition of the P≡C bond across the V≡Ct Bu moiety, followed by a reductive decarbonylation to form the V-C≡O linkage. The nature of the electronic ground state in diamagnetic complexes, 2 and 4, was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X-ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X-ray single-crystal structural characterization. In combination, these data are consistent with a low-valent vanadium ion in complexes 2 and 4. This study represents the first example of a metathesis reaction between the P-atom of [PCO]- and an alkylidyne ligand.
| S-EPMC8559866 | biostudies-literature
Project description:We report an unusual series of discrete iodosyl- and iodoxyarene adducts of Co. The formation of these adducts was confirmed by a suite of techniques including single crystal X-ray diffraction. The reactivity of these adducts with O-atom acceptors and an H-atom donor has been investigated with particular focus on elucidating mechanistic details. Detailed kinetic analysis allows for discrimination between proposed oxo and adduct mediated mechanisms. In particular, these reactions have been interrogated by competition experiments with isotopically labelled mixtures which shows that all of the studied adducts display a large KIE. These studies suggest different mechanisms may be relevant depending on subtle substituent changes in the adduct complexes. Reactivity data are consistent with the involvement of a transient oxo complex in one case, while the two other systems appear to react with substrates directly as iodosyl- or iodoxyarene adducts. These results support that reactivity typically ascribed to metal-oxo complexes, such as O-atom transfer and C-H activation, can also be mediated by discrete transition metal iodosyl- or iodoxyarene adducts that are frequent intermediates in the generation of oxo complexes. The influence of additional Lewis acids such as Sc3+ on the reactivity of these systems has also been investigated.
| S-EPMC5958341 | biostudies-literature
Project description:Phosphine oxides and arsine oxides are common laboratory reagents with diverse applications that stem from the chemistry exhibited by these monomeric species. Stibine oxides are, in contrast, generally dimeric or oligomeric species because of the reactivity-quenching self-association of the highly polarized stiboryl (Sb=O/Sb+-O-) group. We recently isolated Dipp3SbO (Dipp = 2,6-diisopropylphenyl), the first example of a kinetically stabilized monomeric stibine oxide, which exists as a bench-stable solid and bears an unperturbed stiboryl group. Herein, we report the isolation of Mes3SbO (Mes = mesityl), in which the less bulky substituents maintain the monomeric nature of the compound but unlock access to a wider range of reactivity at the unperturbed stiboryl group relative to Dipp3SbO. Mes3SbO was found to be a potent Lewis base in the formation of adducts with the main-group Lewis acids PbMe3Cl and SnMe3Cl. The accessible Lewis acidity at the Sb atom results in a change in the reactivity with GeMe3Cl, SiMe3Cl, and CPh3Cl. With these species, Mes3SbO formally adds the E-Cl (E = Ge, Si, C) bond across the unsaturated stiboryl group to form a 5-coordinate stiborane. The biphilicity of Mes3SbO is sufficiently potent to activate even the C-F and Si-F bonds of C(p-MeOPh)3F and SiEt3F, respectively. These results mark a significant contribution to an increasingly rich literature on the reactivity of polar, unsaturated main-group motifs. Furthermore, these results highlight the utility of a kinetic stabilization approach to access unusual bonding motifs with unquenched reactivity that can be leveraged for small-molecule activation.
| S-EPMC11258792 | biostudies-literature
Project description:We present an extension of the all-atom internal-coordinate force field, ICMFF, that allows for simulation of heterogeneous systems including hexopyranose saccharides and glycan chains in addition to proteins. A library of standard glycan geometries containing α- and β-anomers of the most common hexapyranoses, i.e., d-galactose, d-glucose, d-mannose, d-xylose, l-fucose, N-acetylglucosamine, N-acetylgalactosamine, sialic, and glucuronic acids, is created based on the analysis of the saccharide structures reported in the Cambridge Structural Database. The new force field parameters include molecular electrostatic potential-derived partial atomic charges and the torsional parameters derived from quantum mechanical data for a collection of minimal molecular fragments and related molecules. The ϕ/ψ torsional parameters for different types of glycosidic linkages are developed using model compounds containing the key atoms in the full carbohydrates, i.e., glycosidic-linked tetrahydropyran-cyclohexane dimers. Target data for parameter optimization include two-dimensional energy surfaces corresponding to the ϕ/ψ glycosidic dihedral angles in the disaccharide analogues, as determined by quantum mechanical MP2/6-31G** single-point energies on HF/6-31G** optimized structures. To achieve better agreement with the observed geometries of glycosidic linkages, the bond angles at the O-linkage atoms are added to the internal variable set and the corresponding bond bending energy term is parametrized using quantum mechanical data. The resulting force field is validated on glycan chains of 1-12 residues from a set of high-resolution X-ray glycoprotein structures based on heavy atom root-mean-square deviations of the lowest-energy glycan conformations generated by the biased probability Monte Carlo (BPMC) molecular mechanics simulations from the native structures. The appropriate BPMC distributions for monosaccharide-monosaccharide and protein-glycan linkages are derived from the extensive analysis of conformational properties of glycoprotein structures reported in the Protein Data Bank. Use of the BPMC search leads to significant improvements in sampling efficiency for glycan simulations. Moreover, good agreement with the X-ray glycoprotein structures is achieved for all glycan chain lengths. Thus, average/median RMSDs are 0.81/0.68 Å for one-residue glycans and 1.32/1.47 Å for three-residue glycans. RMSD from the native structure for the lowest-energy conformation of the 12-residue glycan chain (PDB ID 3og2) is 1.53 Å. Additionally, results obtained for free short oligosaccharides using the new force field are in line with the available experimental data, i.e., the most populated conformations in solution are predicted to be the lowest energy ones. The newly developed parameters allow for the accurate modeling of linear and branched hexopyranose glycosides in heterogeneous systems.
| S-EPMC4431507 | biostudies-literature
Project description:Metalation of secondary diaminophosphine boranes by alkali metal amides provides a robust and selective access route to a range of metal diaminophosphide boranes M[(R2 N)2 P(BH3 )] (M=Li, Na, K; R=alkyl, aryl) with acyclic or heterocyclic molecular backbones, whereas reduction of a chlorodiaminophosphine borane gave less satisfactory results. The metalated species were characterized in situ by NMR spectroscopy and in two cases isolated as crystalline solids. Single-crystal XRD studies revealed the presence of salt-like structures with strongly interacting ions. Synthetic applications of K[(R2 N)2 P(BH3 )] were studied in reactions with a 1,2-dichlorodisilane and CS2 , which afforded either mono- or difunctional phosphine boranes with a rare combination of electronegative amino and electropositive functional disilanyl groups on phosphorus, or a phosphinodithioformate. Spectroscopic studies gave a first hint that removal of the borane fragment may be feasible.
| S-EPMC7756230 | biostudies-literature