The reaction of tetraphenyldiphosphazane (Ph2P)2NH with mesityl azide 2,4,6‐Me3C6H2‐N3 affords a new [N,N′] chelating ligand, [HN(Ph2PN(2,4,6‐Me3C6H2))2] (LH). The ligand can be easily deprotonated by using nBuLi or Li[N(SiMe3)2] in Et2O to yield [{N(Ph2PN(2,4,6‐Me3C6H2))2}Li·OEt2] (1). The reaction of LH with AlMe3 and BH3·SMe2, respectively, gives the corresponding mononuclear complexes [{N(Ph2PN(2,4,6‐Me3C6H2))2}AlMe2] (2) and a rare borondihydride [{N(Ph2PN(2,4,6‐Me3C6H2))2}BH2] (3). Similarly, reaction of 1 with the trihalides, MX3, of group 13 elements afford the corresponding dihalo complexes, [{N(Ph2PN(2,4,6‐Me3C6H2))2}MX2] [M = B, X = F (4); M = Al, X = Cl (5); M = Ga, X = Cl (6); M = In, X = Br (7)]. All the complexes reported in this work have been isolated in good yields and are expected to serve as useful synthons in a number of reactions. The solid‐state structure of LH and 1–7 have been investigated by single‐crystal X‐ray structural analysis.

Hydrosilylation of C=C double and C≡C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. We report here the synthesis of...

The reaction of a recently synthesized dihydroboron species complexed with bis(phosphinimino)amide, LBH2 (), (L = [N(Ph2PN(2,4,6-Me3C6H2))2](-)) with 3 equivalents of BH2Cl·SMe2 or one equivalent of BCl3 affords the first stable monohydridoborenium ion, [LBH](+)[HBCl3](-) () that is stable without a weakly coordinating bulky anion. Compound can also be prepared directly by refluxing LH with 3 equivalents of BH2Cl·SMe2. Interestingly, reaction of LBH2 () with elemental sulfur and selenium involves oxidative addition of S and Se into B-H bonds and subsequent release of H2S (or H2Se) from the intermediate LB(SH)2 (or LB(SeH)2) species forming stable compounds with terminal boron-chalcogen double bonds LB[double bond, length as m-dash]S () and LB[double bond, length as m-dash]Se (). The electronic structures of compounds , and were elucidated by high resolution mass spectrometry, multi-nuclear NMR and single crystal X-ray diffraction studies. Ab initio calculations on are in excellent agreement with its experimental structure and clearly support the existence of the boron-sulfur double bond.

An air‐stable dicationic Zn2+ complex (1) in a tripod‐type ligand with non‐bound phosphorus base and three pyridinyl “arms” (TPPh) was synthesized. Remarkably, while 2 mol% of 1 at room temperature selectively catalyzed dehydrogenative borylation of terminal alkynes with HBPin, a lower loading of 1 (0.5 mol%) at 90 °C selectively promoted hydroboration reaction of the same alkynes skipping the dehydrogenative borylation step. The mode of action of 1 was proposed based on experimental observations as well as the mechanism of dehydrogenative borylation was studied by DFT computations.

Reactions of bis(phosphinimino)amines LH and L'H with Me2 S⋅BH2 Cl afforded chloroborane complexes LBHCl (1) and L'BHCl (2), and the reaction of L'H with BH3 ⋅Me2 S gave a dihydridoborane complex L'BH2 (3) (LH=[{(2,4,6-Me3 C6 H2 N)P(Ph2 )}2 N]H and L'H=[{(2,6-iPr2 C6 H3 N)P(Ph2 )}2 N]H). Furthermore, abstraction of a hydride ion from L'BH2 (3) and LBH2 (4) mediated by Lewis acid B(C6 F5 )3 or the weakly coordinating ion pair [Ph3 C][B(C6 F5 )4 ] smoothly yielded a series of borenium hydride cations: [L'BH](+) [HB(C6 F5 )3 ](-) (5), [L'BH](+) [B(C6 F5 )4 ](-) (6), [LBH](+) [HB(C6 F5 )3 ](-) (7), and [LBH](+) [B(C6 F5 )4 ](-) (8). Synthesis of a chloroborenium species [LBCl](+) [BCl4 ](-) (9) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH2 (4) with three equivalents of BCl3 . It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three-coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl4 (-) can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4-dimethylaminopyridine (DMAP), [LBH⋅(DMAP)](+) [B(C6 F5 )4 ](-) (10). The solid-state structures of complexes 1, 5, and 9 were investigated by means of single-crystal X-ray structural analysis.

FLP-type Si–H bond activation by carbonyls in 1,2-dibenzoyl-o-carborane leading to new hydrofuranes with an o-carboranyl backbone in a self-catalyzed reaction.

In this work the first examples of C−N bond activation by insertion into the geometrically constrained PIII-centre are shown. The mechanisms of these activation processes leading to new PV species...

Paramagnetic metal complexes gained a lot of attention due to their participation in a number of important chemical reactions. In most cases, these complexes are dominated by 17-e metalloradicals that are associatively activated with highly reactive paramagnetic 19-e species. Molybdenum paramagnetic complexes are among the most investigated ones. While some examples of persistent 17-e Mo-centered radicals have been reported, in contrast, 19-e Mo-centered radicals are illusive species and as such could rarely be detected. In this work, the photodissociation of the [Cp(CO) 3 Mo] 2 dimer ( 1 ) in the presence of phosphines was revisited. As a result, the first persistent, formally 19-e Mo radical with significant electron density on the Mo center (22%), Cp(CO) 3 Mo • PPh 2 ( o -C 2 B 10 H 11 ) ( 5b ), was generated and characterized by EPR spectroscopy and MS as well as studied by DFT calculations. The stabilization of 5b was likely achieved due to a unique electron-withdrawing effect of the o -carboranyl substituent at the phosphorus center.