The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ3-P compound in the hexaphenyl-carbodiphosphoranyl-based pincer-type ligand (1+) are reported. 1+ reacts with electron-poor fluoroarenes via an oxidative addition-type reaction C-F bond to PIII-center, yielding new fluorophosphorane-type species (PV). This was used catalytic hydrodefluorination Ar-F bonds PhSiH3, C-N bond-forming cross-coupling reactions between aminosilanes. Importantly, these closely mimics...

A geometrically constrained phosphenium cation in bis(pyrrolyl)pyridine based NNN pincer type ligand (1

Geometrically constrained, square pyramidal phosphoranide was synthesized, and its reactivity study showed that it is both a nucleophile reductant.

Abstract An air‐stable dicationic Zn 2+ complex ( 1 ) in a tripod‐type ligand with non‐bound phosphorus base and three pyridinyl “arms” (TPPh) was synthesized. Remarkably, while 2 mol% of at room temperature selectively catalyzed dehydrogenative borylation terminal alkynes HBPin, lower loading (0.5 mol%) 90 °C promoted hydroboration reaction the same skipping step. The mode action proposed based on experimental observations as well mechanism studied by DFT computations.

Abstract We report here a new route for the preparation of [1,1′‐bis( o‐ carboranyl)]borane, 3D analogue 9‐borafluorene, η 2 ‐ σ‐ silane adduct ( 1‐H‐SiEt 3 ) in high yields (>80 %). The nature B−H−Si bonding was studied by density functional theory (DFT) computations. Preliminary reactivity study with small molecules carried out. Interestingly, reacts benzophenone hexane producing deoxygenation product Ph CH . While benzene, leading to mixture and (3 : 1). is formed via addition benzene...

Two equivalents of 1-benzyl-3-bromoethylbenzimidazolium bromide couple with Na2Se to produce the first selenoether bridged bis-benzimidazolium salt (LH2)Br2. The nitrate (LH2)(NO3)2 and tetrafluoroborate (LH2)(BF4)2 salts were also synthesized from reaction Hg(OAc)2 (LH2)Br2 gave pseudo pincer carbene mercury complex, [Hg(L-κ2C)][HgBr4] (C1). Different complexes Pd(ii) obtained using (LH2)(NO3)2. Syntheses these dependent on counter anion temperature. Thus, type ionic complex...

Reduction of the cyclodiphosphazane [(S=)ClP(μ-NtBu)]2 (1) with sodium metal in refluxing toluene proceeds via two different pathways. One is a Wurtz-type pathway involving elimination NaCl from 1 followed by head-to-tail cyclization to give hexameric macrocycle [(μ-S)P(μ-NtBu)2 P(=S)]6 (2). The other involves reduction P=S bonds generate colorless singlet biradicaloid dianion trans-[S-P(Cl)(μ-NtBu)]2 (2-) , which observed polymeric structures three-dimensional [{(S-)ClP(μ-NtBu)2...

In this work the first examples of C-N bond activation by insertion into a geometrically constrained PIII-centre are shown. The mechanisms these processes leading to new PV species were studied both experimentally and computationally. Interestingly, in case an N-C(O)H bond, unstable phosphoranyl-formaldehyde intermediate is probably formed, which undergoes decarbonylation presence catalytic amount HCl producing hydrophosphorane.

[cAAC·HgBr(μ-Br)]₂ catalyzed intermolecular hydroamination of phenylacetylenes with anilines has been demonstrated under mild conditions.

Borazine is isoelectronic with benzene and popularly referred to as inorganic benzene. The study of non-covalent interactions borazine comparison its organic counterpart promises show interesting similarities differences. motivation the present borazine-water interaction, for first time, stems from such possibilities. Hydrogen-bonded complexes water were studied using matrix isolation infrared spectroscopy quantum chemical calculations. Computations performed at M06-2X MP2 levels theory...

The reactivity of a bicyclic (alkyl)(amino)carbene (BICAAC) towards different boranes has been examined in the present work. reactions with BX3·SMe2 (X = H, Cl, Br), BF3·OEt2 and BCl3 yield Lewis adducts [BICAAC·BH3] (1), [BICAAC·BHCl2] (2), [BICAAC·BH2Cl] (3), [BICAAC·BF3] (4), [BICAAC·BCl3] (5) [BICAAC·BBr3] (6) respectively, whereas more hydridic boranes, 9-borabicyclo[3.3.1]nonane (9-BBN) catecholborane (HBcat), enable insertion carbene carbon into B-H bond to form [BICAAC(H)-(9-BBN)]...

Main-group compounds that can mimic the behavior of transition-metal (TM) complexes are great interest due to their potential in TM-free catalysis. Here, we report synthesis, isolation and full characterization geometrically constrained phosphenium cation with 2,6-bis(o-carborano)pyridine pincer-type ligand. A preliminary reactivity study showed this is capable activating H−H bond by a formal oxidative addition PIII cationic center, which unprecedented for PIII-centers, producing new...

Abstract The reaction of tetraphenyldiphosphazane (Ph 2 P) NH with mesityl azide 2,4,6‐Me 3 C 6 H ‐N affords a new [ N , N′ ] chelating ligand, [HN(Ph PN(2,4,6‐Me )) ( LH ). ligand can be easily deprotonated by using n BuLi or Li[N(SiMe ) in Et O to yield [{N(Ph }Li · OEt 1 AlMe and BH SMe respectively, gives the corresponding mononuclear complexes }AlMe rare borondihydride }BH Similarly, trihalides, MX group 13 elements afford dihalo complexes, }MX [M = B, X F 4 ); M Al, Cl 5 Ga, In, Br 7...

Coordination induced bond weakening (CIBW) leads to facile PCET at various E–H bonds.

Abstract New In(III) complexes with iminophosphonamide ligand are reported for the first time. Reaction of lithium iminophosphonamide, LLi⋅2OEt 2 InCl 3 afforded heterobimetallic compound, LInCl(μ‐Cl) Li⋅2OEt ( 1 ) (L=(2,6‐iPr C 6 H N)P(Ph )(NtBu)). To prevent formation LiCl adduct in , and to obtain targeted LInCl molecule, potassium salt LK was reacted that gave (THF) ). Formation compounds can be considered an outcome centers exhibit Lewis acidity. non coordinating solvent toluene dimer...

Structurally constrained, cationic PIII compound [LP][SbCl4] with an OCO pincer‐type ligand (L) having a central carbene donor was directly synthesized via Sb‐to‐P metathesis reaction between PCl3 and LSb‐Cl. isolated its reactivity small molecules (ROH RNH2) studied, showing that [SbCl4]– is not innocent counter anion, but active participant in these reactions. When the replaced [CB11H12]– ([Cb]–) reactions were redirected to [LP]+ cation only. The alcohols amines led equilibrium products...

Structurally constrained, cationic PIII compound [LP][SbCl4] with an OCO pincer‐type ligand (L) having a central carbene donor was directly synthesized via Sb‐to‐P metathesis reaction between PCl3 and LSb‐Cl. isolated its reactivity small molecules (ROH RNH2) studied, showing that [SbCl4]– is not innocent counter anion, but active participant in these reactions. When the replaced [CB11H12]– ([Cb]–) reactions were redirected to [LP]+ cation only. The alcohols amines led equilibrium products...

Donor–acceptor interactions (Npy⋯E) have been utilized to assemble conformationally rigid [3.3](2,6)pyridinophanes containing group 13 elements.

Molecular topologies varying from simple complexes to pyridinophanes (neutral and cationic) bicyclic pyridinophane containing organoaluminum (Al-Me) species were synthesized by the relative stoichiometry of bis(trimethylsilyl)-N,N'-2,6-diaminopyridine (bap) reactive partner (AlMe3). The ultimate goal these reactions was systematically design cyclic structures group 13 elements. To highlight reaction potential shapes, bowl-shaped reacted with Lewis acid, B(C6F5)3, generate a stable cationic...

Abstract Invited for the cover of this issue is group Sanjay Singh and Dominic S. Wright at Indian Institute Science Education Research in Mohali Cambridge University. The image depicts a sulfur‐bridged hexameric inorganic macrocycle along with stable 2D 3D polymeric arrangements singlet biradicaloid dianion. Read full text article 10.1002/chem.201600839 .

We have demonstrated stepwise functionalization of chlorophosph(III)azane, [ClP(µ-NtBu)]2 with organic azides and chalcogens (S Se). The in situ 31P{1H} NMR spectroscopic investigations reveal that conversion the basic PIII2N2 framework, leading to PV2N2 proceeds via (PIII/PV)N2 intermediates. Under controlled conditions, intermediate species can be isolated, providing details reaction pathway distribution cis trans isomers products. It has also been neat reactions at elevated temperatures...

An unexpected rearrangement occurred when an imidazolinium based OCO pincer-type ligand (1) reacted with PCl3 producing a chlorophosphine pendant oxazolium "arm" (3). The mechanism of this was studied both experimentally and by density functional theory (DFT) computations. deprotonation 3 led to further results.