Sai Manoj Gorantla N V T

UiT The Arctic University of Norway · Centre for Theoretical and Computational Chemistry

Dinitrogen and dihydrogen ligated metal complexes [(L)nM−H2/N2] have been known to chemists for nearly four decades. These species are captivating for their unusual bonding interactions between transition metal atoms and closed-shell diatomic molecules like H2/N2. Some of these complexes are part of the textbook, with emphasis given to their surpri...

Silicon compounds containing a variety of unusual oxidation states within the same molecule are quite important, because their high reactivity leads to the formation of a variety of silicon compounds....

The boracarboxylation reaction has potential for the production of natural products and drug candidates, but the development of an asymmetric version of this transformation is challenging. We report an enantioselective boracarboxylation of styrenes, enabled by a copper catalyst containing chiral phosphines. Our experimental conditions provide yield...

Silicon is one of the most important components of electronic devices. Surface passivation of a silicon wafer is an active area of research. The Si(OH)2 sites of partially oxidized silicon surface could exist as hydroxylated [Si(OH)2] or hydrated silanone [SiO∙(OH2)]. The previously reported disiladicarbene (cAAC)2Si2 has been reacted here with wat...

Herein, we report the synthesis of a rare bis‐silylene, 1, in which two SiIIatoms are bridged by a SiIV atom. Compound 1 contains an unusual SiII−SiIV−SiII bonding arrangement with SiII−SiIV bond distances of 2.4212(8) and 2.4157(7) Å. Treatment of 1 with Fe(CO)5 afforded a dinuclear Fe⁰ complex 2 with two unusually long Si−Si bonds (2.4515(8) and...

Electrochemical nitrogen reduction reaction (NRR) for producing NH 3 (ammonia) is a suitable alternative to the Haber-Bosch process due to its eco-friendly and non-polluting nature. Herein, we report a homogeneous Ni-based...

The cover image is based on the Research Article Stability and bonding of carbon(0)‐iron N2 complexes relevant to nitrogenase cofactor: EDA‐NOCV analyses by Sai Manoj N. V. T. Gorantla et al., https://doi.org/10.1002/jcc.27012

Two new series of air stable compounds of cAACX = fluorene/indene (X = Me2, Et2, Cy) [cAAC = cyclic (alkyl) amino carbene] have been isolated and well characterized by X‐ray single crystal diffraction, photoluminescence, cyclic voltammogram (CV) and electron paramagnetic resonance (EPR) studies. Fluorescence studies reveals green light emission of...

The factors/structural features which are responsible for the binding, activation and reduction of N2 to NH3 by FeMoco of nitrogenase have not been completely understood well. Several relevant model complexes by Holland et al. and Peters et al. have been synthesized, characterized and studied by theoretical calculations. For a matter of fact, those...

The FeVco cofactor of nitrogenase (VFe7S8(CO3)C) is an alternative in the molybdenum (Mo)-deficient free soil living azotobacter vinelandii. The rate of N2 reduction to NH3 by FeVco is a few times higher than that by FeMoco (MoFe7S9C) at low temperature. It provides a N source in the form of ammonium ions to the soil. This biochemical NH3 synthesis...

Metal ions‐based inorganic‐organic hybrid composites are often reported acting as good to excellent catalysts with various substrate scopes under milder reaction conditions. The active catalyst of a catalytic cycle is sometimes proposed to be a short‐lived reactive intermediate species. A three coordinate (L‐Me)Ni(II) intermediate species [L−Me = O...

Arenes [C6H3R(TMS)(OTf); also called benzyne/aryne precursors] containing inter‐related leaving groups Me3Si (TMS) and CF3SO3(OTf) on the adjacent positions (1,2‐position) are generally converted to their corresponding aryne‐intermediates via the addition of fluoride anion (F−) and subsequent elimination of TMS and OTf groups. This reaction is be...

Binding of dinitrogen (N2) to a transition metal center (M) and followed by its activation under milder conditions is no longer impossible; rather, it is routinely studied in laboratories by transition metal complexes. In contrast, binding of N2 by main group elements has been a challenge for decades, until very recently, an exotic cAAC‐borylene (c...

A series of possible precursors for generating C 2 with the general formula Me 3 E–C 2 –I(Ph)FBF 3 [E = C ( 1 ), Si ( 2 ), and Ge ( 3 )] has been theoretically investigated using quantum chemical calculations. The equilibrium geometries of all species show a linear E–C 2 –I ⁺ backbone. The inspection of the electronic structure of the Me 3 E–C 2 bo...

Recently, dinitrogen (N2) binding and its activation have been achieved by non-metal compounds like intermediate cAAC-borylene as (cAAC)2(B-Dur)2(N2) [cAAC = cyclic alkyl(amino) carbene; Dur = aryl group, 2,3,5,6-tetramethylphenyl; B-Dur = borylene]. It has attracted a lot of scientific attention from different research areas because of its future...

Metal complexes containing low valence iron atoms are often experimentally observed to bind with the dinitrogen (N2) molecule. This phenomenon has attracted the attention of industrialists, chemists and bio-chemists since these N2-bonded iron complexes can produce ammonia under suitable chemical or electrochemical conditions. The higher binding aff...

(Tip)2SbCl (1, Tip = 2,4,6-triisopropylphenyl) has been utilized as a precursor for the synthesis of the distibane (Tip)4Sb2 (4) via one-electron reduction using KC8. The two-electron reduction of 1 and 4 afforded the novel trinuclear antimonide cluster [K3((Tip)2Sb)3(THF)5] (6). Changing the reducing agent from KC8 to a different alkali metal resu...

Dinitrogen (N2) binding and electron transfer reduction of N2 to ammonia (NH3) by the FeMoco cofactor of the nitrogenase enzyme are captivating. They are a part of the textbook for general chemistry. The nature of N2 bonding by reduced FeMoco is speculated based on the experimental evidence. The inorganic core MoFe7S9C¹⁻ possesses a Fe6(μ6‐C⁴⁻) uni...

The binding of the dinitrogen molecule to the metal center is the first and crucial step toward dinitrogen activation. Favorable interaction energies are desired by chemists and biochemists to study model complexes in the laboratory. An electrochemically reduced form of a previously isolated sulfur-bridged Ni3S8 complex is inferred to bind N2 at mu...

The MoFe7S9C1– unit of the nitrogenase cofactor (FeMoco) attracts chemists and biochemists due to its unusual ability to bind aerial dinitrogen (N2) at ambient condition and catalytically convert it into ammonia (NH3). The mode of N2 binding and its reaction pathways are yet not clear. An important conclusion has been made based on the very recent...

The Donor base ligand-stabilized cyclopentadienyl-carbene compounds L−C 5 H 4 (L = H 2 C, aAAC; (CO 2 Me) 2 C, Py; aNHC, NHC, PPh 3 ; SNHC; aAAC = acyclic alkyl(amino) carbene, aNHC = acyclic N-hetero cyclic carbene, NHC = cyclic N-hetero cyclic carbene, SNHC = saturated N-hetero cyclic carbene, Py = pyridine) (1a-1d, 2a-2c, 3) have been theoretica...

The cover image is based on the Full Paper Stabilization of group 14 elements E = C, Si, Ge by hetero-bileptic ligands cAAC, MCOn with push-pull mechanism Sai Manoj N. V. T. Gorantla, Pattiyil Parameswaran, and Kartik Chandra Mondal., https://doi.org/10.1002/jcc.26530.

The stability and bonding of a series of hetero-diatomic molecules with general formula (cAAC)EM(CO)n , where cAAC = cyclic alkyl(amino) carbene; E = group 14 elements (C, Si, and Ge); M = transition metal (Ni, Fe, and Cr) have been studied by quantum chemical calculations using density functional theory (DFT) and energy decomposition analysis-nat...

Syntheses of the copper and gold complexes [Cu{Fe(CO)5}2][SbF6] and [Au{Fe(CO)5}2][HOB{3,5‐(CF3)2C6H3}3] containing the homoleptic carbonyl cations [M{Fe(CO)5}2]⁺ (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu2Fe, Ag2Fe and Au2Fe complexes [Cu{Fe(CO)5}2][SbF6], [Ag{Fe(CO)5}2][SbF6] and [Au{Fe(CO)5}2][HOB{3,5‐(CF3)2C6H3}3] are...

The donor base ligand stabilized compound (L)2C6F4 [1 for L=saturated N‐heterocyclic carbene (SNHCDip) and 2 for L=cyclic alkyl(amino) carbene (cAACMe)] has been investigated by energy decomposition analysis (EDA) coupled with natural orbital for chemical valence (NOCV) calculation. The bonding analysis of 1 has revealed that (SNHCDip)2⁺ prefers to...

Fluoro- and chloro-phosphasilynes [X–SiP (X = F, Cl)] belong to a class of illusive chemical species which are expected to have SiP multiple bonds. Theoretical investigations of the bonding and stability of the corresponding Lewis base-stabilized species (L′)PSi(X)(L) [L′ = cAACMe (cyclic alkyl(amino) carbene); L = cAACMe, NHCMe (N-heterocyclic car...

Alkali metal salts of carbene‐supported phosphinidenides were obtained by the reductive dehalogenation of carbene‐stabilized chloro‐phosphinidene precursors in THF. Structural elucidations in solution and solid state reveals the existence of the dimeric phosphinidenide anions exclusively in THF solution, whereas in the solid state oligomerization t...

Quantum chemical calculations using density functional methods were performed for complexes of type L2C2 with L = NHCMe (1), SNHCMe (2) (S = saturated), cAACMe (3), and diamidocarbene (DACMe) (4). The equilibrium structures of 1-4 possess almost linear C4 cores. A high thermochemical stability of the complexes with respect to dissociation, L2C2 → C...

Cyclic alkyl(amino) carbene (cAAC)‐supported, structurally diverse alkali metal‐phosphinidenides 2–5 of general formula ((cAAC)P‐M)n(THF)x [2: M=K, n=2, x=4; 3: M=K, n=6, x=2; 4: M=K, n=4, x=4; 5: M=Na, n=3, x=1] have been synthesized by the reduction of cAAC‐stabilized chloro‐phosphinidene cAAC=P‐Cl (1) utilizing metallic K or KC8 and Na‐naphthale...

The syntheses of the two novel complexes [Ag{Mo/W(CO)6}2]⁺[F‐{Al(ORF)3}2]⁻ (RF=C(CF3)3) are reported along with their structural and spectroscopic characterization. The X‐ray structure shows that three carbonyl ligands from each M(CO)6 fragment bend towards the silver atom within binding Ag−C distance range. DFT calculations of the free cations [Ag...

Quantum chemical studies using density functional theory and ab initio methods have been carried out for the molecules L‐C3‐L with L=PPh3 (1), NHCMe (2, NHC=N‐heterocyclic carbene), and cAACMe (3, cAAC=cyclic (alkyl)(amino) carbene). The calculations predict that 1 and 2 have equilibrium geometries where the ligands are bonded with rather acute bon...

Density functional theory calculations at the M06-D3/def2-TZVPPD level of the group-13 anion complexes EFe(CO) 3 − (E = B-Tl) and the isoelectronic neutral and charged boron adducts BTM(CO) 3 q (TM q = Fe − , Ru − , Os − , Co, Rh, Ir, Ni + , Pd + , Pt +) give tetrahedral (C 3v) geometries in the 1 A 1 electronic ground state as equilibrium structur...

This work reports isolation of three multinuclear complexes of Dy(III) ion ([DyIII2(L‐NO2)2(Ph3PO)2(NO3)2] (1), [DyIII5(L)6(Ph3PO)(NO3)(H2O)2(μ3‐OH)2] (2), [DyIII6(L–CH3)6(Ph3PO)2 (μ3‐OH)3(NO3)2 (CH3OH)2] (3)]) by controlling substitution on ligand molecule. The reactions of substituted Schiff‐base ligands (H2L−R; R=NO2 (1), R=H (2), R=CH3 (3)), tr...

A Schiff-base nickel(II)-phosphene-catalyzed chemodivergent C-H functionalization and cyclopropanation of aromatic heterocycles is reported in moderate to excellent yields and very good regioselectivity and diastereoselectivity. The weak, noncovalent interaction between the phosphene ligand and Ni center facilitates the ligand dissociation, generat...

Chemistry of coinage metal ions with Fe(CO)5, [Mn(CO)5]⁻ and [Fe(CO)4CN]⁻ have been explored using Mes3P and N-heterocyclic carbene supporting ligands. A comparison of [(SIPr)Au-Fe(CO)5][SbF6], [(Et2CAAC)Au-Fe(CO)5][SbF6] and [(Mes3P)Au-Fe(CO)5][SbF6] shows that the ligand donor strength towards Au(I) follows the order Mes3P > Et2CAAC > SIPr. These...

A series of six hetero‐bimetallic complexes having umbrella shape topology and general formula (L)2CuLn(NO3)(Ph3PO) have been synthesized by reacting a methanolic solution of diprotic ligand (H2L) [(E)‐2‐(((2‐hydroxyphenyl)imino)methyl)‐6‐methoxyphenol] and co‐ligand Ph3P=O with CuCl2.2H2O and Ln(NO3)3⋅6H2O (Ln= Gd(1), Tb(2),Dy(3), Ho(4), Er(5) and...

Two novel 3d (Ni)/4 f (Dy and Y) metal ions and polydentate organic ligands (H2L1 and H2L2) based tetranuclear coordination complexes, [(L1)4NiII2DyIII2(DMF)2(NO3)2]⋅DMF (1) and [(L2)4NiII2YIII2(DMF)2(NO3)2]⋅DMF⋅H2O (2), have been synthesized and characterized using IR, elemental analysis and single crystal X‐ray diffraction studies. The applicatio...

Zn(II) Schiff base complexes are good precursors for preparation of ZnO nanoparticles which find several biomedical applications. Herein, a fluorescent hexanuclear Zn(II) Schiff base complex [Zn(II)6(L−Me)6(MeOH)2]⋅12MeOH(1) [H2L‐Me=diprotic Schiff base ligand] has been synthesized and characterized by single crystal X‐ray diffraction, NMR spectros...

The existence of a metal‐metal bond in organometallic and coordination complexes is a very important aspect. Metal‐carbonyl, carbene‐metal‐carbonyl and metal‐carbene complexes were studied for having this feature. Herein, an air stable dark green color dicobalt coordination complex [Co(III)2(hep)3(N3)3] (1) [hepH = 2‐(2‐ethylhydroxy)pyridine] with...

Effect of structural modification of sal fatty acid-based branched mono- and polyol esters on lubricant properties was explored. In an attempt to improve the pour point of the sal fatty acid- based lubricant base stocks, enrichment of unsaturation in sal fat was carried out using urea adduct complexation method. Oleic acid rich (73.2% by GC) sal fa...

Thumba seed oil, a minor, renewable tree borne oil, was exploited for the preparation of bio-lubricant base-stocks. The different base-stocks prepared were epoxy thumba oil (ETO), branched, 2-ethylhexyl ester (T2-EtHE), and polyol esters, namely, neopentyl glycol (TNPGE), trimethylolpropane (TTMPE) and pentaerythritol (TPEE) esters of thumba fatty...

Apocynin (4-hydroxy-3-methoxy acetophenone), a well known phytochemical, was converted to its oxime and further esterified with fatty acids of different chain lengths (C4-C18) to obtain the oxime esters in about 80% yields. The structures of the oxime esters were confirmed using NMR, IR and mass spectroscopy. The prepared oxime esters of fatty acid...

Sal fat, a nontraditional seed oil, was chemically modified to obtain base stocks with a wide range of specifications that can replace mineral oil base stocks. Sal fatty acids were enriched to 72.6% unsaturation using urea adduct method and reacted with branched mono alcohol, 2-ethylhexanol (2-EtH), and polyols namely neopentyl glycol (NPG) and tri...