A theoretical study on the alkene insertion step in Rh-Yanphos catalyzed hydroformylation

This paper studied the mechanism of the alkene insertion elementary step in the asymmetric hydroformylation （AHF） catalyzed by RhH（CO）2[（R,S）-Yanphos] using four alkene substrates （CH2=CH- Ph, CH2=CH-Ph-（p）-Me, CH2=CH-C（==O）OCH3 and CH2=CH-OC（=O）-Ph, abbreviated as A1-A4）. Interestingly, the equatorial vertical coordination mode （A mode） with respect to the Rh center was found for AI and A2 but not for A3 and A4, although the equatorial in-plane coordination mode （E mode） was found for A1 -A4. The relative energy of the E mode of the -q2-intermediates is lower than that of the A mode. In the alkene insertion step, Path 1 is more favorable than Path 2 for this system. As for AI and A2, there could be a transformation between 2eq and 2ax.     

1,1-Bis(trifluoromethyl)butadiene-1,3—A new fluorinated building block

Although 1,1-bis(trifluoromethyl)butadiene-1,3 (1) reacts with dimethylamine with selective formation of 1,4-adduct [trans-(CF₃)₂CHCHCHCH₂N(CH₃)₂], halogenation of 1 proceeds with predominant formation (>92%) of 1,2-adducts (CF₃)₂CCHCHXCH₂X (X = Cl or Br). Electrophilic conjugated addition of “ClF” or “BrF” to 1 proceeds exclusively with the formation of 1,2-adducts (CF₃)₂CCHCHFCH₂X (major) and (CF₃)₂CCHCHXCH₂F (X = Cl or Br). Difluorocarbene adds selectively to CHCH₂ moiety of 1 forming thermally stable vinylcyclopropane. In Diels-Alder reaction with linear or cyclic dienes (butadienes, cyclopentadiene, cyclohexadiene-1,3) and quadricyclane compound 1 behaves as dienophile providing for the reaction electron-deficient CHCH₂ bond. The relative rate of cycloaddition of 1 and other fluoroolefins to quadricyclane, measured by high temperature NMR, indicates that (CF₃)₂CCH acts as very strong electron-withdrawing substituent. Synthetic utility of products based on 1 was also demonstrated.     

The structure and two-dimensional correlation infrared spectroscopy study of a new 2D polyoxomolybdate complex containing β-octamolybdate linked up by potassium ions: (4,4′-Hbpy)2(K2Mo8O26)

A novel compound, (4,4′-Hbpy)₂(K₂Mo₈O₂₆) 1 (bpy = bipydine), was synthesized by hydrothermal method and characterized by X-ray single analysis, thermalgravimetric analysis, one-dimensional (1D) infrared spectroscopy and two-dimensional (2D) correlation infrared spectroscopy under thermal perturbation. In the compound 1, the [Mo₈O₂₆] units link to potassium ions to form layer structure, and the protonated 4,4′-bpy are linked to chains by hydrogen bonds. The 2D IR correlation spectroscopy study indicates that the intensity changes of MoO, NH and CC stretching vibration are sensitive to the temperature variation, and the intensity changes of asymmetry stretching vibration of the terminal MoO occur prior to that of terminal MoO linked by K atom. At the same time, the peaks of asymmetry stretching vibrations of the terminal MoO and the stretching vibrations of NH split into two peaks respectively in 2D IR correlation spectroscopy.     

Nitrogen- and oxygen-bridged bidentate phosphaalkene ligands

An overview is given on synthesis and structures of new bidentate phosphaalkene ligands [(RMe₂Si)₂CP]₂E (E = O, NR, N^?) and (RMe₂Si)₂CPN(R′)PR′′₂. Exceptional properties of these ligands, extending beyond predictable properties of phosphaalkenes are: (i) the NSi bond cleavage of [(iPrMe₂Si)₂CP]₂NSiMe₃ with Au^I and Rh^I chloro complexes under mild conditions leading to binuclear complexes of the 6π-delocalised imidobisphosphaalkene anion [(iPrMe₂Si)₂CP]₂N^?, and (ii) the chlorotropic formation of molecular 1:2 Pd^II and Pt^II metallochloroylid complexes with novel ylid-type ligands [(RMe₂Si)₂CP(Cl)N(R)PR₂]^?, and the transformation of a P-platina-P-chloroylid complex into a C-platina phosphaalkene by intramolecular chlorosilane elimination. Properties of the heavier congeners [(RMe₂Si)₂CP]₂E (E = S, Se, Te, PR, P^?, As^?) and (RMe₂Si)₂CPEPR′′₂ (E = S, Se, Te) are also described.     

CuLn complexes with a single μ-oximato bridge

Two original dinuclear (LnYb, 3 and LnEr, 4) and one trinuclear Cu^IILn^IIICu^II (LnGd, 5) complexes derived from a polydentate non symmetrical Schiff base ligand H₂L have been prepared. The ligand possesses two functions (phenol and oxime) able to coordinate the Ln ions, but structural studies (X-ray diffraction and powder X-ray diffraction) show that the Cu^II and Ln^III ions are only bridged by the oximato (NO) pair. The missing phenoxo bridge is replaced by a surprising pseudo-bridge involving one oxygen atom of the nitrato anion linked to the Cu and Ln ions according to a η²: η¹: μ mode. Although this latter contact has no role from the magnetic point of view, it introduces a large deformation of the unique bridging network. The CuYb complex 3 and the trinuclear CuGdCu complex 5 present antiferromagnetic interactions, with a J_CuGd interaction equal to ?1.25 cm^?1 in 5. The genuine single bridge can be considered as responsible for the antiferromagnetic character of the interaction.     

Molecular structure of caffeine as determined by gas electron diffraction aided by theoretical calculations

The molecular structure of caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) was determined by means of gas electron diffraction. The nozzle temperature was 185 °C. The results of MP2 and B3LYP calculations with the 6-31G⁷ basis set were used as supporting information. These calculations predicted that caffeine has only one conformer and some of the methyl groups perform low frequency internal rotation. The electron diffraction data were analyzed on this basis. The determined structural parameters (r_g and ∠_α) of caffeine are as follows: <r(NC)_ring> = 1.382(3) Å; r(CC) = 1.382(←) Å; r(CC) = 1.446(18) Å; r(CN) = 1.297(11) Å; <r(NC_methyl)> = 1.459(13) Å; <r(CO)> = 1.206(5) Å; <r(CH)> = 1.085(11) Å; ∠N₁C₂N₃ = 116.5(11)°; ∠N₃C₄C₅ = 121. 5(13)°; ∠C₄C₅C₆ = 122.9(10)°; ∠C₄C₅N₇ = 104.7(14)°; ∠N₉–C₄=C₅ = 111.6(10)°; <∠NCH_methyl> = 108.5(28)°. Angle brackets denote average values; parenthesized values are the estimated limits of error (3σ) referring to the last significant digit; left arrow in parentheses means that this parameter is bound to the preceding one.     

Reaction of the RuTp(PR3)Cl fragment with alkynols: Formation of carbene,vinylidene, allenylidene,and carbyne complexes

The reaction of RuTp(COD)Cl (1) with PR₃ (PR₃ = PPh₂ⁱPr, PⁱPr₃, PPh₃) and propargylic alcohols HCCCPh₂OH, HCCCFc₂OH (Fc = ferrocenyl), and HCCC(Ph)MeOH has been studied.In the case of PR₃ = PPh₂ⁱPr, PⁱPr₃ and HCCCPh₂OH, the 3-hydroxyvinylidene complexes RuTp(PPh₂ⁱPr)(CCHC(Ph)₂OH)Cl (2a) and RuTp(PⁱPr₃)(CCHC(Ph₂)OH)Cl (2b) were isolated.With PR₃ = PPh₂ⁱPr and HCCCFc₂OH as well as with PR₃ = PPh₃ and HCCCPh₂OH dehydration takes place affording the allenylidene complexes RuTp(PPh₂ⁱPr)(CCCFc₂)Cl (3b) and RuTp(PPh₃)(CCCPh₂)Cl (3c).Similarly, with PPh₂ⁱPr and HCCC(Ph)MeOH rapid elimination of water results in the formation of the vinylvinylidene complex RuTp(PPh₂ⁱPr)(CCHC(Ph)CH₂)Cl (4).In contrast to the reactions of the RuTp(PR₃)Cl fragment with propargylic alcohols, with HCC(CH₂)_nOH (n = 2, 3, 4, 5) six-, and seven-membered cyclic oxycarbene complexes RuTp(PR₃)(C₄H₆O)Cl (5), RuTp(PR₃)(C₅H₈O)Cl (6), and RuTp(PR₃)(C₆H₁₀O)Cl (7) are obtained. On the other hand, with 1-ethynylcyclohexanol the vinylvinylidene complex RuTp(PPh₂ⁱPr)(CCHC₆H₉)Cl (8) is formed. The reaction of the allenylidene complexes 3a–c with acid has been investigated. Addition of CF₃COOH to a solution of 3a–c resulted in the reversible formation of the novel RuTp vinylcarbyne complexes [RuTp(PPh₂ⁱPr)(C–CHCPh₂)Cl]⁺ (9a), [RuTp(PPh₂ⁱPr)(C–CHCFc₂)Cl]⁺ (9b), and [RuTp(PPh₃)(C–CHCPh₂)Cl]⁺ (9c). The structures of 3a, 3b, and 5b have been determined by X-ray crystallography.     

The Raman spectra of serine and 3,3-dideutero-serine in aqueous solution

The Raman spectra of serine [α-amino-β-hydroxypropionic acid; HOCH₂CH(NH₃)⁺COO⁻] and 3,3-dideutero-serine [HOCD₂CH(NH₃)⁺COO⁻] in aqueous solution were studied in the range 4000–300 cm⁻¹. The data obtained for the deuterated compound are novel and provide compelling evidence that previously reported assignments for the undeuterated amino acid should be revised.     

Theoretical calculations of the substituent effect on molecular properties of the RCN⋯HF hydrogen-bonded complexes with R = NH2, CH3O,CH3, OH,SH, H,Cl, F,CF3, CN and NO2

DFT calculations with B3LYP and PBE1PBE functionals and 6–311++G(d,p) basis set have been performed in order to obtain molecular geometries, binding energies and vibrational properties of the RCN?HF H-bonded complexes with R = NH₂, CH₃O, CH₃, OH, SH, H, Cl, F, CF₃, CN and NO₂. As expected, it has been verified as a red-shift of the HF stretching frequency (ν_HF), in conformity with the elongation of the bond after complexation. On the other hand, the CN stretching frequency (ν_CN) is blue-shifted and corresponds to a shortening of the bond. The binding energies (ΔE_c), including BSSE and ZPVE corrections, show a linear correlation with several structural, electronic and vibrational properties. In particular, an important linear dependence between the binding energy and the calculated dipole moment of the free RCN molecule (μ_RCN) has been found. This result suggests that μ_RCN can be a useful quantity in order to predict the ability of this fragment to form a hydrogen-bond. The IR intensities of stretching and bending modes of complexed HF acid fragment are adequately interpreted through the atomic polar tensor of the hydrogen atom in HF using the modified CCFO model for infrared intensities. The new vibrational modes arising from complexation show several interesting features.     

DFT study of the IR and Raman spectra of a fluorescent dendron built from cyclotriphosphazene core

Combined experimental and theoretical studies on molecular structure of the zero generation dendron, built from the hexafunctional cyclotriphosphazene core, with five OC₆H₄(CH₂)₂NHSO₂C₁₀H₆N(CH₃)₂ terminal groups and one oxybenzaldehyde group G₀ are reported. The Fourier transform Raman and IR spectra of G₀ have been recorded. Conformations of low energy isomers of G₀ have been studied at quantum-chemical level. The optimized geometry has been calculated by density functional (DFT) method at the PBE/TZ2P level of theory. The theoretical geometrical parameters, harmonic vibrational frequencies, IR intensities and Raman scattering activities are predicted in a good agreement with the experimental data. It was found that dendron molecule G₀ has a concave lens structure with planar OC₆H₄CHO fragments and slightly non-planar cyclotriphosphazene core. Relying on DFT calculations the bands of the core and terminal groups were assigned. The frequencies of ν(NH) bands in the IR spectrum reveal the presence of the H-bonds in the dendron.     

CH⋯Ni interactions and cyano-bridged heteronuclear polymeric complexes studied by vibrational spectroscopy and quantum chemistry calculations

Three 1D bimetallic M(II)/Ni(II) (M = Cu, Zn and Cd) complexes, [Cu(OHepy)₂Ni(CN)₄]_n (1), [Zn(OHepy)₂Ni(CN)₄]_n (2) and [Cd(OHepy)₂Ni(CN)₄]_n (3) (2-(2-hydroxyethyl)pyridine abbreviated to OHepy), have been synthesized and characterized by FT-IR and Raman spectroscopy, elemental, thermal analyses and single crystal X-ray diffraction techniques. FT-IR and Raman spectra of OHepy have been experimentally and theoretically investigated in the region of 4000–250 cm⁻¹. The corresponding vibrational assignments of OHepy are examined by means of B3LYP hybrid density functional theory (DFT) method together with 6-311++G(d, p) basis set. Moreover, reliable vibrational assignments have been made on the basis of potential energy distribution (PED). The structures of the complexes consist of one-dimensional polymeric chain M(OHepy)₂NCNi(CN)₂CNM(OHepy)²⁻, in which the M(II) and Ni(II) atoms are linked by CN groups. The nickel atom is fourfold coordinated with four cyanide-carbon atoms in a square planar arrangement and the metal(II) atoms are sixfold coordinated with two cyanide nitrogen, two OHepy nitrogen and two OHepy oxygen atoms, in a distorted octahedral arrangement. In all the complexes adjacent chains are connected by π⋯π, CH⋯Ni and OH⋯N hydrogen bonding interactions to form two and three dimensional networks.     

1,3-Dipolar cycloaddition of diaryldiazomethanes across N-ethoxy-carbonyl-N-(2,2,2-trichloroethylidene)amine and reactivity of the resulting 2-azabutadienes towards thiolates and cyclic amides

1,3-dipolar cycloaddition of diaryldiazomethanes Ar₂CN₂ across Cl₃C–CHN–CO₂Et 1 yields Δ³-1,2,4-triazolines 2. Thermolysis of 2 leads, via transient azomethine ylides 3, to diaryldichloroazabutadienes [Ar(Ar')CN–CHCCl₂] 4. Treatment of 4a (Ar = Ar' = C₆H₅) and 4c (Ar = Ar' = p-ClC₆H₄) with NaSR in DMF yields 2-azabutadienes [Ar₂CN–C(H)C(SR)₂] 5. In contrast, nucleophilic attack of NaStBu on 4 affords azadienic dithioethers [Ar₂CN–C(S^tBu)C(H)(S^tBu)] (7a Ar = C₆H₅; 7b Ar' = p-ClC₆H₄). The reaction of 4a with NaSEt conducted in neat EtSH produces [Ph₂CN–C(H)(SEt)–CCl₂H] 8, which after dehydrochloration by NaOMe and subsequent addition of NaSEt is converted to [Ph₂CN–C(SEt)C(H)(SEt)] 7c. Upon the reaction of 4c with NaSⁱPr, the intermediate dithioether [(p-ClC₆H₄)₂CN–CHC(SⁱPr)₂] 5k is converted to tetrakisthioether [(p-ⁱPrSC₆H₄)₂CN–CHC(SⁱPr)₂] 6. Treatment of 4a with the sodium salt of piperidine leads to [Ph₂CN–CHC(NC₅H₁₀)₂] 10. The coordination of 6 on CuBr affords the macrocyclic dinuclear Cu(I) complex 11. The crystal structures of 5i, 7a,b, 10 and 11 have been determined by X-ray diffraction.     

Synthesis,molecular structure and reactivity of new π-conjugated diyne with ferrocenyl and phenyl units

New π-conjugated butadiynyl ligand FcC(CH₃)₂Fc′–CC–CC–Ph (L₁) has been synthesized and its reaction with Co₂(CO)₈ has been studied. New clusters [FcC(CH₃)₂Fc′–CC–CC–Ph][Co₂(CO)₆]_n [(1): n = 1; (2): n = 2] and [Fc–CC–CC–Ph][Co₂(CO)₆]_n [(3): n =  1; (4): n = 2] were obtained by the reaction of ligands FcC(CH₃)₂Fc′–CC–CC–Ph (L₁) and Fc–CC–CC–Ph (L₂) with Co₂(CO)₈ respectively and the composition and structure of the clusters and ligands have been characterized by elemental analysis, FTIR, ¹H and ¹³C NMR and MS. The crystal structures of compounds L₁, L₂, 2 and 4 have been determined by X-ray single crystal analysis.     

The effects of hydrogen on KOH activation of petroleum coke

KOH activation of petroleum coke (PC) was conducted with 30 vol%H₂ + 70 vol% N₂ as carrier gas. TG-DTG, FTIR, elemental analysis, N₂ adsorption, GC and XRD techniques were used to investigate the effects of hydrogen on the activation. During the initial stage of the activation, i.e. the carbonization of the PC, additional CH and CH₂ species were formed due to the chemisorption of hydrogen on the nascent sites of the PC created by the removal of the surface heteroatom groups. The formation of the CH and CH₂ species increased the quantity of ‘active sites’ which is favorable to the further activation reaction, and developed the porous structure of the activated carbons. The micropore volume and BET surface areas of the activated carbon prepared under 30 vol% H₂ + 70 vol% N₂ and with a relatively low KOH/PC weight ratio of 2:1 have been increased from 0.78 cm³/g and 1936 m²/g to 0.97 cm³/g and 2477 m²/g, respectively, compared to that prepared in pure N₂ atmosphere with the same KOH/PC ratio.     

Metal-(phenylthio)alkanoic acid interactions— VII. The crystal and molecular structures of diaquabis[(benzylthio)acetato]-zinc(II), catena- [diaqua-tetra[(benzylthio)acetato]-bis[cadmium(II)], catena-tetra-μ-{2-methyl-3- (phenylthio)propionato-O,O′]-bis[copper(II)]} and tetra-μ-[2-methyl-2-(phenylthio)propionato-O,O′]- bis[ethanolcopper(II)]

The crystal structures of diaquabis[(benzylthio)acetato]zinc(II), [Zn(BTA)₂ (H₂O)₂] (1), catena-[diaqua-tetra[(benzylthio)acetato)]-bis[cadmium(II)], [Cd₂(BTA)₄ H₂O)₂]_n (2), catena-{tetra-μ-[2-methyl-3-(phenylthio)propionato-O,O′]-bis[copper (II)]}, [Cu₂(MPTP)₄]_n (3) and tetra-μ-[2-methyl-2-(phenylthio)propionato-O,O′]- bis[ethanol copper(II)], [Cu₂(PTIBA)₄(EtOH)₂] (4) have been determined using X-ray diffraction techniques. Complex (1) is monomeric with distorted octahedral stereochemistry and lies on a two-fold rotational axis. The MO₆ coordination involves four oxygens from two slightly asymmetric bidentate BTA car☐yl groups [ZnO, 2.138(3), 2.28(3)Å] and two cis-related waters [ZnOw, 1.996(3)Å]. The cadmium complex (2) is best described in terms of a polymer with the repeating unit consisting of two different centres, one seven, the other six-coordinate. With the first, the distorted MO₆S coordination sphere has four oxygens from two asymmetric bidentate car☐ylate groups (ligands B and C) [CdO, 2.36, 2.56(1)Å; 2.26, 2.67(1)Å], an oxygen and a sulphur from a bidentate chelate ligand (A) [CdO, 2.36(1)Å; CdS, 2.773(4)Å] and an oxygen from a bridging car☐yl group (ligand D) [CdO, 2.28(1)Å]. Ligands C and D also bridge two Cd centres through sulphurs [CdS, 2.739, 2.723(4)Å]. The second car☐yl oxygen of ligand A also forms a bridge to the second Cd [(CdO, 2.30(1)Å], while the distorted octahedral MO₄S₂ stereochemistry is completed by two waters [CdO, 2.25(1), 2.49(1)Å] and a sulphur from ligand D [CdS, 2.723(4)Å] giving a polymer structure. Complexes (3) and (4) are centrosymmetric tetra-car☐ylate bridged dimers [for (3) Cu ··· Cu, 2.586(3)Å; mean CuO(equatorial), 1.957(11)Å; for the two independent dimers in (4), Cu ··· Cu, 2.596(1), 2.616(1)Å; CuO (equatorial), 1.952(4), 1.968(4)Åmean]. The axial positions of the dimer in (3) are occupied by car☐yl oxygens of adjacent dimers [CuO, 2.280(9)Å] forming a polymer structure. In contrast, these positions in (4) are occupied by ethanol molecules with CuO, 2.222(3) and 2.177(4)Årespectively for the two independent dimers.     

Continous gradient temperature Raman Spectroscopy identifies flexible sites in proline and alanine peptides

Continuous gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near phase transitions. Herein we apply GTRS and DSC to the solid dipeptides Ala-Pro, Pro-Ala, and the mixture Ala-Pro/Pro-Ala 2:1. A simple change in residue order resulted in dramatic changes in thermal stability and properties. Characteristic Pro vibrations were observed at ∼75 °C higher temperature in Pro-Ala than Ala-Pro. The appearance/disappearance of characteristic vibrational modes with increasing temperature showed that a double peak in the Ala-Pro major phase transition (174–184 °C) was due to a gauche to anti 165° rotation of H₃CC*NH₃ about C*. CH₂ rocking and wagging frequencies present in Pro-Ala were not observed in Ala-Pro. For Ala-Pro, the Ala ⁺NH_3, and Pro COO⁻ sites were flexible whereas the Pro ring moiety was not; since the OCN (C)₂ amide bond is planar the CNC moiety keeps the Pro ring rigid. For Pro-Ala, CH₂ sites in the Pro ring were flexible and the OCNH amide bond is perpendicular to the Pro ring. Since the mass of the Pro ring is significantly larger than the mass of the flexible Ala ⁺NH₃ moiety, Pro-Ala absorbs more thermal energy, corresponding to a higher phase transition temperature (240–260 °C). Ala-Pro, Pro-Ala, and Ala-Pro/Pro-Ala 2:1 exhibited α-helix, β-sheet, α-helix secondary structure conformations, respectively.     

Cyanate ester resin/graphene nanocomposite: Curing dynamics and network formation

The curing dynamics and network formation of cyanate ester resin/graphene oxide (GO) nanocomposites were studied by means of Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FT-IR) and Raman spectroscopies. The incorporation of GO into the resin showed a strong catalytic effect on the cure of the resin, especially in the initial stages. Addition of 4 wt.% GO resulted in the decrease of curing temperature significantly about 97 °C. Activation energy of the nanocomposites also maintained at a low level till the end of the cure. The most effective catalytic behavior was observed with 1 wt.% GO. Both FT-IR and Raman spectra revealed that OH group in GO reacted with cyanate group OCN in the resin to form O(CNH)O bond in the early stages of the cure. These results could provide a low temperature curing route for cyanate ester resins with improved curing efficiency.     

Generation of a substituted 1,2,4-thiadiazole ring via the [3+2] cycloaddition reaction of benzonitrile sulfide toward trichloroacetonitrile. A DFT study of the regioselectivity and of the molecular mechanism

A theoretical study of the [3+2] cycloaddition (32CA) reaction between benzonitrile sulfide BNS1 and trichloroacetonitrile TCAN2 at the MPWB1 K/6-311G(d) level was undertaken. Among two feasible C1N5 and C1C4 regioisomeric channels, the former is completely preferred, in the presence of toluene, over the latter, both kinetically, ΔΔG_activation = 17.5 kcal/mol, and thermodynamically, ΔΔG_reaction = –12.8 kcal/mol, in excellent agreement with experimental outcomes. The strong global electrophilic and nucleophilic characters found for TCAN2 and BNS1, respectively, allow the studied 32CA reaction to take place via a polar process. Interestingly, the analysis of the TSs geometries clarifies that in the case under study, regioselectivity is controlled by destabilizing steric repulsion interactions rather than electronic ones. The ELF topological patterns indicate that while the formation of S3C4 single bond takes place exactly according to Domingo's model, that of the C1N5 single bond is a direct consequence of the nucleophilic attack of the C5 carbon atom on the N5 nitrogen atom supporting a two-stage one-step molecular mechanism.     

Rh（Ⅱ） carbene S-H insertion into H2S via the stepwise mechanism

The mechanism of Rh(Ⅱ)carbene S-H insertion into H_2S in gas phase has been studied by B3LYP functional.Calculation results showed that the Rh(Ⅱ)carbene S-H insertion into H_2S took only stepwise channels and no concerted channels had been located, which was different from the Rh(Ⅱ)carbene C-H and O-H insertions.     

In silico quest for stable phosphastannaallenes

A computational study at different levels of theory was performed for the not yet synthesized phosphastannaallenes >SnCP– in order to evaluate the strength of the SnC bond, the main postulated factor to stabilize such species, and the geometry in R₂SnCPR derivatives. The influence of the substituents with various electronic effects (H, Me, Ph, F, Cl, OMe, SiMe₃) at the Sn or P atoms of the SnCP unit on the SnC bond order was evaluated in the quest for a substituent that would stabilize the phosphastannaallenic unit. PC bond orders have also been calculated.