The reaction of [LAlH2 ] (L=HC(CMeNAr)2 , Ar=2,6-iPr2 C6 H3 ) with MeOTf (Tf=SO2 CF3 resulted in the formation [LAlH(OTf)] (1) high yield. triflate substituent 1 increases positive charge at aluminum center, which implies that has a strong Lewis acidic character. excellent catalytic activity for hydroboration organic compounds carbonyl groups was investigated. Furthermore, it shown effectively initiates addition trimethylsilyl cyanide (TMSCN) to both aldehydes and ketones. Quantum mechanical...

The well-defined aluminum dihydride LAlH2 (L = HC(CMeNAr)2, Ar 2,6-Et2C6H3) (1) operates in catalysis like a transition metal complex. catalytic activity of 1 for hydroboration terminal alkynes was investigated. Furthermore, catalyst effectively initiated the dehydrocoupling boranes with amines, thiols, and phenols, respectively, to form compounds B-E bonds (E N, S, O) under elimination H2. Quantum mechanical calculations indicate that reactions occur via three consecutive cycloaddition...

Abstract The bisadduct (cAAC) 2 Ni II Cl [ 1 ; cAAC = cyclic (alkyl)(amino)carbene] was directly synthesized by treating with NiCl . Compound reduced to 0 ( ) using lithium diisopropylamide or KC 8 Crystals of were stable under an inert gas for several months and decomposed upon heating above 165 °C. On the basis calculated natural bond orbital charge values nickel atom in , oxidation state determined be between I (+0.34). Theoretical calculations suggested a closed‐shell singlet electronic...

Abstract The reaction of [LAlH 2 ] (L=HC(CMeNAr) , Ar=2,6‐ i Pr C 6 H 3 ) with MeOTf (Tf=SO CF resulted in the formation [LAlH(OTf)] ( 1 high yield. triflate substituent increases positive charge at aluminum center, which implies that has a strong Lewis acidic character. excellent catalytic activity for hydroboration organic compounds carbonyl groups was investigated. Furthermore, it shown effectively initiates addition trimethylsilyl cyanide (TMSCN) to both aldehydes and ketones. Quantum...

Abstract The trapping of a silicon(I) radical with N‐heterocyclic carbenes is described. reaction the cyclic (alkyl)(amino) carbene [cAAC Me ] (cAAC =:C(CMe 2 ) (CH )NAr, Ar=2,6‐ i Pr C 6 H 3 SiI in 3:1 molar ratio DME afforded mixture separated ion pair [(cAAC Si: . + I − ( 1 ), which features cationic cAAC–silicon(I) radical, and −H] In addition, NHC–iodosilicon(I) dimer [I Ar (I)Si:] (I =:C{N(Ar)CH} 4 equiv (:C{N(Me)CMe} proceeded through formation intermediate, [(I SiH] comprising first...

The cyclic alkyl(amino) carbene (cAAC) 1 reacted with SiI4 in toluene, affording the cAAC-silicon tetraiodide complex [(cAACMe)SiI4] (2, cAACMe = :C(CH2)(CMe2)2NAr, Ar 2,6-iPr2C6H3). It further two equivalents of KC8 toluene at room temperature to afford first cAAC-diiodosilylene [(cAACMe)SiI2] (3). DFT calculations show that Ccarbene-Si bond 3 is formed by donation lone pair electrons on Ccarbene atom SiI2 moiety, while π-back-bonding Si negligible. presence silicon also evidenced its...

Cationic terminal borylene complexes, synthesized by halide abstraction, offer a versatile platform on which to gauge the effects electronic structure of metal−ligand bond brought about variation in substituent and metal/ligand framework. While exerts strong influence boron-centered electrophilicity hence π character length (e.g., from 1.792(8) Å for [Cp*Fe(CO)2(BMes)]+ 2.049(4) [CpFe(CO)2{B(NCy2)(4-pic)}]+), much smaller changes are effected set. Introduction stronger donor ruthenium-...

The electronic structure and reactivity of neutral tricoordinated Be(0) compounds BeL3, L = CO (1), NHC (2) PMe3 (3) are explored by quantum mechanical calculations. These BeL3 complexes found to be planar or nearly like electron deficient BH3 but isoelectronic with NH3 possess three L→Be donor–acceptor bonds. Be atom can considered as sp2-hybridized a lone pair in the highly diffused 2pz-orbital contrast sp3 hybridization NH3. Even though on is stabilized through π-back donation...

Cr(i)Cl is a very unstable species. The present work describes the stabilisation of in low coordinate environment cyclic alkyl(amino) carbene ligands and its synthetic application to yield an unprecedented cationic complex with two Cr(i). One electron reduction (cAAC)2CrCl2 (1) equivalent amount KC8 results formation (cAAC)2CrCl (2), distorted trigonal planar configuration at metal centre. SQUID, EPR theoretical studies reveal Cr(i) centre S = 5/2 spin ground state for 2. It represents first...

Isolation of the first Si(<sc>ii</sc>) supported dinuclear Au(<sc>i</sc>) cation with an intramolecular Au⋯Au interaction 2.875(1) Å has been realized.

The reactions of terminal borylene complexes the type [CpFe(CO)2(BNR2)]+ (R = iPr, Cy) with heteroallenes have been investigated by quantum-chemical methods, in an attempt to explain experimentally observed product distributions. Reaction dicyclohexylcarbodiimide (CyNCNCy) gives a bis-insertion product, which 1 equiv carbodiimide is assimilated into each Fe═B and B═N double bonds form spirocyclic boronium system. In contrast, isocyanates (R′NCO, R′ Ph, 2,6-Xyl, Cy; Xyl C6H3Me2) react give...

Thermally induced chemoselective borylene transfer from [(OC)(5)Mo=BN(SiMe(3))(2)] (2a) to the carbon-carbon triple bond of an iron dicarbonyl alkynyl complex [(η(5)-C(5)Me(5))Fe(CO)(2)C≡CPh] (3) led isolation aminoborirene [(η(5)-C(5)Me(5))(OC)(2)Fe{μ-BN(SiMe(3))(2)C=C}Ph] (4) in satisfactory yield. Room temperature photolysis 4 resulted unprecedented rearrangement and a concurrent decarbonylation, affording novel C(2) side-on coordinated boryl...

Abstract Crystallographic studies of the fluorinated tetraarylporphyrin 5,10,15,20‐tetrakis(2′,3′,5′,6′‐tetrafluoro‐ N , ‐dimethyl‐4‐anilinyl)porphyrin and its metal complexes [MTF 4 DMAP; M = 2H · 2 O, 1 ; Ni II THF, Cu 5H 3 Zn (THF) THF tetrahydrofuran] are reported. To analyse weak intermolecular interactions, we have used a combination energy decomposition analysis Hirshfeld surface analysis, which allowed us to elucidate nature various close contacts. The shows that dispersive...

Abstract Compound (Me 2 ‐cAAC:) Co 0 ( ; Me ‐cAAC:=cyclic (alkyl) amino carbene; :C(CH )(CMe ) N‐2,6‐ i Pr C 6 H 3 was synthesized by the reduction of precursor I Cl 1 with KC 8 in THF. The cyclic voltammogram exhibited one‐electron reduction, which suggests that synthesis a bent 2‐metallaallene from should be possible. contains one cobalt atom formal oxidation state zero, is stabilized two ‐cAAC: ligands. Bond lengths X‐ray diffraction are 1.871(2) and 1.877(2) Å C‐Co‐C bond angle...

Abstract Photocatalysis on pristine g‐C 3 N 4 (CN) often suffers from fast recombination of photogenerated electrons and holes. Herein, we demonstrate the superior photocatalytic performance free base tetrakis(4‐carboxyphenyl) porphyrin (TCPP) – (CN/TCPP) hybrids synthesised by a facile ultrasound aided impregnation. Structural morphological characterisation confirmed successful formation hybrid via noncovalent π–π stacking. Optical/electrochemical characterisation, as well DFT study,...

Here, we present the synthesis, photochemical, and DNA binding properties of three photoisomerizable azobenzene−distamycin conjugates in which two distamycin units were linked via electron-rich alkoxy or electron-withdrawing carboxamido moieties with azobenzene core. Like parent A, these molecules also demonstrated AT-specific binding. Duplex abilities found to depend upon nature length spacer, location protonatable residues, isomeric state conjugate. The changes duplex efficiency individual...

Diberyllium hydride complex – not a diborane analogue: the diberyllium hydrides Be₂(CH₃)₂H₂L₂(L = H⁻, CO, NHC and CN⁻) are isostructural to but differ in nature of bonding interaction at bridging H-atoms.

Synthesis of a metal-free carbon nitride (g-C3N4) photocatalyst in the form nitrogen-rich g-C3–xN4+x derivatives is desirable for efficient solar to hydrogen conversion and remains challenging task achieve. Herein we report development homogeneous sheets graphitic samples from melamine by solid–gas interface approach. Using this method, pure g-C3N4 (CN), under ammonia flow (CN-NH3) nitrogen (CN-N2) are prepared. The sample shows better surface conductivity, wide optical absorbance visible...

The EDA-NOCV analysis shows that the singlet 2-adamantylidene is a foiled-type carbene stabilized by hyperconjugative interaction of one pair vicinal C–C σ-MOs with empty p-orbital on carbon atom. high proton affinity and hydride indicate ambiphilic nature 2-adamantylidene.

Abstract The trapping of a silicon(I) radical with N‐heterocyclic carbenes is described. reaction the cyclic (alkyl)(amino) carbene [cAAC Me ] (cAAC =:C(CMe 2 ) (CH )NAr, Ar=2,6‐ i Pr C 6 H 3 SiI in 3:1 molar ratio DME afforded mixture separated ion pair [(cAAC Si: . + I − ( 1 ), which features cationic cAAC–silicon(I) radical, and −H] In addition, NHC–iodosilicon(I) dimer [I Ar (I)Si:] (I =:C{N(Ar)CH} 4 equiv (:C{N(Me)CMe} proceeded through formation intermediate, [(I SiH] comprising first...

The electronic structure and reactivity of heteroleptic divalent group 14 compounds, 1E (E=C-Sn) with NHC cAAC ligands have been studied at the BP86/TZ2P level theory compared homoleptic compounds. EDA-NOCV (energy decomposition analysis-natural orbitals for chemical valence) analysis indicates that interaction between two carbene central C-atom in 1C can be best represented as one 3c-2e electron sharing σ-bond donor-acceptor σ-bond. There exists an π-type orbital on C-N π* a π-back-donation...

Electronic structure of the six-membered N-heterocyclic carbene, silylene, germylene, and stannylene having an exocyclic double bond at C3 carbon atom as well relative reactivity lone-pair on divalent group 14 element have been studied BP86 level theory with a TZVPP basis set. The geometrical parameters, NICS values, NBO population analysis indicate that these molecules can be best described localized 1Xa, where trans-butadiene (C1–C2–C3–C4) unit is connected diaminocarbene (N1–X–N2) via...