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...

Oxidative insertion of sulfur or selenium into the B–H bonds, bis(phosphinimino)amide stabilized dihydroboron species, followed by H₂S H₂Se evolution leads to a facile access stable thioxo- and selenoxo-boranes.

An air-stable, Zn²⁺-based catalyst for catalytic hydrosilylation reactions of alkenes and alkynes.

Abstract Reactions of bis(phosphinimino)amines LH and L′H with Me 2 S ⋅ BH Cl afforded chloroborane complexes LBHCl ( 1 ) L′BHCl ), the reaction 3 gave a dihydridoborane complex L′BH (LH=[{(2,4,6‐Me C 6 H N)P(Ph )} N]H L′H=[{(2,6‐ i Pr N]H). Furthermore, abstraction hydride ion from LBH 4 mediated by Lewis acid B(C F 5 or weakly coordinating pair [Ph C][B(C ] smoothly yielded series borenium cations: [L′BH] + [HB(C − [B(C [LBH] 7 8 ). Synthesis chloroborenium species [LBCl] [BCl 9 without...

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.

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...

Paramagnetic metal complexes gained a lot of attention due to their participation in number important chemical reactions. In most cases, these are dominated by 17-e metalloradicals that associatively activated with highly reactive paramagnetic 19-e species. Molybdenum among the investigated ones. While some examples persistent Mo-centered radicals have been reported, contrast, illusive species and as such could rarely be detected. this work, photodissociation [Cp(CO)3Mo]2 dimer (1) presence...

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...

The activation of Si-H bonds is a very important transformation both in organic and inorganic chemistry. Herein we report that 1,2-dibenzoyl-o-carborane (1) reacts with bonds, yielding new hydrofurane-type products. mechanism this bond was studied experimentally by DFT calculations, supposedly proceeds an FLP-type manner.

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

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...

The difference in reactivity of 1,2-dibenzoyl-o-carborane (2) and its analogue with an aromatic backbone two C6F5 electron withdrawing groups, C6H4(CO(C6F5))2 (5), cyclization reactions R3SiH (R = Et, Ph (a)) or without a catalytic amount B(C6F5)3 was studied. In contrast to the reaction 2 R3SiH, which directly leads cyclic hydrofurane products 3 4, 5 do not react B(C6F5)3. However, presence B(C6F5)3, reacts forming through hydrofurane-type 9, 9a, isobenzofuran 6. 2, on other hand, giving...

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.

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