Single-phase melem (2,5,8-triamino-tri-s-triazine) C6N7(NH2)3 was obtained as a crystalline powder by thermal treatment of different less condensed C−N−H compounds (e.g., melamine C3N3(NH2)3, dicyandiamide H4C2N4, ammonium dicyanamide NH4[N(CN)2], or cyanamide H2CN2, respectively) at temperatures up to 450 °C in sealed glass ampules. The crystal structure determined ab initio X-ray diffractometry (Cu Kα1: P21/c (No. 14), = 739.92(1) pm, b 865.28(3) c 1338.16(4) β 99.912(2)°, and Z 4). In the...

The first [ECE]Ni(II) pincer complexes with E = Si(II) and Ge(II) metallylene donor arms were synthesized via C-X (X H, Br) oxidative addition, starting from the corresponding [EC(X)E] ligands. These novel fully characterized (NMR, MS, XRD) used as catalyst for Ni-catalyzed Sonogashira reactions. catalysts allowed detailed information on elementary steps of this catalytic reaction (transmetalation → addition reductive elimination), resulting in isolation characterization an unexpected...

Breaking the donor limits: The remarkable coordination chemistry of ECHE (E=Si, Ge) ligands with Group 9 metals (Ir, Rh) and their application in catalytic CH borylation arenes was investigated. spectroscopic structural features first [ECE] iridium complexes show stronger σ-donating properties divalent Si Ge pincer compared to analogous PIII-based ligands.

From the inside out: Hollow ferrocenyl coordination polymer microspheres with microporous shells were prepared by a convenient and template-free approach. An Ostwald ripening mechanism is responsible for formation of hollow cavities. The hierarchically have potential applications in catalysis, drug delivery, hydrogen storage.

The first electron-rich N-heterocyclic silylene (NHSi)-iron(0) complexes are reported. synthesis of the starting complex is accomplished by reaction Fe(0) precursor [(dmpe)2Fe(PMe3)] 1 (dmpe =1,2-bis(dimethylphosphino)ethane) with chlorosilylene LSiCl (L = PhC(N(t)Bu)2) 2 to give, via Me3P elimination, corresponding iron [(dmpe)2Fe(←:Si(Cl)L)] 3. Reaction in situ generated 3 MeLi afforded [(dmpe)2Fe(←:Si(Me)L)] 4 under salt metathesis reaction, while its Li[BHEt3] yielded...

SiCSi to pick up a metal: A bis(silylene) pincerlike arene 1 (see scheme) has been synthesized through salt metathesis reaction of the dilithium 2,4-di-tert-butyl-resorcinolate with respective chloro silylene precursor [LSiCl]. Remarkably, reacts Pd(PPh3)4 in molar ratio 2:1 under loss all phosphine ligands give pincer complex 2. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made...

Abstract The nickel‐catalyzed decomposition of formic acid to yield molecular hydrogen and the hydrogenation bicarbonate as a carbon dioxide mimic have been examined. Well‐defined nickel complexes modified by PCP‐pincer ligand, especially hydride formate complexes, revealed catalytic activity with turnover numbers up 626 (decomposition) 3000 (hydrogenation). Thus, formal storage release cycle performed well‐defined catalyst was accomplished.

The first N-donor-stabilized phosphasilene LSi(SiMe(3))═PSiMe(3) (L = PhC(NtBu)(2)) has been synthesized in 87% yield through 1,2-silyl migration of the (Me(3)Si)(2)P-substituted, N-heterocyclic silylene [LSi-P(SiMe(3))(2)]. Remarkably, latter reacts with dichlorotriphenylphosphorane Ph(3)PCl(2) to give unprecedented 4π-electron Si(2)P(2)-cycloheterobutadiene [(LSi)(2)P(2)] two-coordinate phosphorus atoms. striking molecular structures as well (29)Si and (31)P NMR spectroscopic features both...

Abstract Aluminum chalcogenides are mostly encountered in the form of bulk aluminum oxides that structurally diverse but typically consist networks with high lattice energy which chalcogen atoms bridge metal centres. This makes their molecular congeners difficult to synthesize because a pronounced tendency for oligomerization. Here we describe isolation monotopic chalcogenide (L Dip N)AlTe(L Et ) 2 =1,3-(2,6-diisopropylphenyl)-imidazolin-2-imine, L...

Abstract Homoaromatic compounds possess an interrupted π system but display aromatic properties due to through-space or through-bond interactions. Stable neutral homoaromatic hydrocarbons have remained rare and are typically unstable. Here we present the preparation of a class stable molecules, supported by experimental evidence (ring current observed NMR spectroscopy equalization bond lengths X-ray structure analysis) computational analysis via nucleus-independent chemical shifts (NICS)...

Abstract A regioselective silylium‐ion‐promoted thiosilylation of internal C−C triple bonds with control over the double bond geometry is described. Both a C(sp 2 )−S and )−Si are formed trans relationship in this two‐component reaction an alkyne thiosilane. The resulting orthogonally functionalized can be chemoselectively defunctionalized or further processed by cross‐coupling reactions alkene configuration retained. procedure also applicable to regio‐ diastereoselective terminal allenes...

The first donor-stabilized tetrasilacyclobutadiene dication species has been synthesized and fully characterized. Its unexpected formation occurs by the Lewis acid assisted reaction of N-heterocyclic chloro silylene [L(Si:)Cl] (L = PhC(NtBu)(2); amidinate) with Cp*ZrCl(3) (Cp* pentamethylcyclopentadienyl) in molar ratio 3:2. Remarkably, four-membered Si(4) core consists two N-donor stabilized silylium subunits silylene-like moieties. dicationic charge is somewhat delocalized on core, which...

Donor–acceptor trumps: The chlorosilyliumylidene salt 2 with a three-coordinate silicon(II) atom is accessible through ligand exchange between NHCSiCl2 and the electron-rich bis(ylide) 1. cation in represents donor-stabilized form of elusive [ClSi:] could be fully characterized, including X-ray diffraction analysis. Oxidation elemental sulfur furnished 3 as sole product.

Herein, the iron-catalyzed reduction of a variety alkynes with silanes as reductant has been examined. With straightforward catalyst system composed diiron nonacarbonyl and tributyl phosphane, excellent yields chemoselectivities (>99%) were obtained for formation corresponding alkenes. After studying reaction conditions, scope limitations reaction, several attempts undertaken to shed light on mechanism.

The silicon analogues of an acylium ion, namely, sila-acylium ions 2a and 2b [RSi(O)(NHC)2]Cl stabilized by two N-heterocyclic carbenes (NHC = 1,3,4,5-tetramethylimidazol-2-ylidene), having chloride as a countercation were successfully synthesized the reduction CO2 using donor silyliumylidene cations 1a 1b [RSi(NHC)2]Cl (1a, 2a; R m-Ter 2,6-Mes2C6H3, Mes 2,4,6-Me3C6H2 1b, 2b; Tipp 2,4,6-iPr3C6H2). Structurally, compound features four coordinate center together with double bond between oxygen...

Abstract The stabilization of the labile, zwitterionic “half‐parent” phosphasilene 4 L′SiPH (L′=CH[(CCH 2 )CMe(NAr) ]; Ar=2,6‐ i Pr C 6 H 3 ) could now be accomplished by coordination with two different donor ligands (4‐dimethylaminopyridine (DMAP) and 1,3,4,5‐tetramethylimidazol‐2‐ylidene), affording adducts 8 9 , respectively. DMAP‐stabilized is capable transferring elusive parent phosphinidene moiety (:PH) to an unsaturated organic substrate, in analogy “free” . Furthermore, compounds...

Abstract The reaction of the bulky bis(imidazolin‐2‐iminato) ligand precursor (1,2‐(L Mes NH) 2 ‐C H 4 )[OTs] ( 1 2+ 2[OTs] − ; L =1,3‐dimesityl imidazolin‐2‐ylidene, OTs= p ‐toluenesulfonate) with lithium borohydride yields boronium dihydride cation N) )BH [OTs] + ) . reacts elemental sulfur to give thioxoborane salt )BS[OTs] 3 ). hitherto unknown compounds , and were fully characterized by spectroscopic methods single‐crystal X‐ray diffraction. Moreover, DFT calculations carried out...

Abstract The ditopic germanium complex FGe(NIPr) 2 Ge[BF 4 ] ( 3 [BF ]; IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) is prepared by the reaction of amino(imino)germylene (Me Si) NGeNIPr 1 ) with BF ⋅OEt . This monocation converted into germylene‐germyliumylidene [BAr F [Ar =3,5‐(CF ‐C 6 H treatment Na[BAr ]. tetrafluoroborate salt reacts equivalents Me SiOTf to give novel (OTf)(GeNIPr) [OTf] [OTf]), which affords and [Al(OR [R =C(CF after anion exchange or Ag[Al(OR ],...

A desymmetrizing silylation of aromatic diols is reported. The previously unknown asymmetric silyl ether formation phenol derivatives achieved by applying List's counteranion directed technique. silylium-ion-like silicon electrophile generated from an allylic silane paired with imidodiphosphorimidate (IDPi) enables enantioselective discrimination achiral 1,1'-biaryl-2,6-diols. enantioselectivity that desymmetrization further improved a downstream kinetic resolution, converting the...

A varied chemistry of ternary and higher phosphorus(v) nitrides has developed during the last few years. However, crystal structure binary nitride P3N5 proved elusive until now. The network built up by PN4 tetrahedra (depicted' on right) resembles that SiO2 Si3N4. Surprisingly, in α-P3N5 are also connected through edge-sharing.

The reaction of bis(2,6-diisopropylphenyl)imidazolin-2-imine (LH, 1) with Me3N·AlH3 furnishes {μ-LAlH2}2 (2). marked tendency 2 to release its hydride substituents is ascribed the strong electron-donor character imidazolin-2-iminato ligand. This supported by reactivity study and DFT calculations. In fact, compound was further converted Me3SiOTf, Me2S·BH3, Me2S·BBr3, BX3 (with X = Cl, Br, I) into {μ-LAl(H)OTf}2 (3), {μ-LAl(BH4)2}2 (4), {μ-LAlX2}2 (5, Br; 6, Cl; 7, I), respectively. For all...

The novel amino(imino)stannylene 1 was prepared by conversion of HNIPr (NIPr = bis(2,6-diisopropylphenyl)imidazolin-2-imino) with one equivalent Lappert's tin reagent (Sn[N(SiMe3)2]2). Treatment DMAP (4-dimethylaminopyridine) yields its Lewis acid-base adduct 2. reaction trimethylsilyl azide results in replacement the amino group at center an N3 substituent concomitant elimination N(SiMe3)3 to afford dimeric [N3SnNIPr]2 (3). Remarkably, B(C6F5)3 produces tin(II) monocation...

The reactions of (dpp-BIAN)Zn−Zn(dpp-BIAN) (1) with PhC≡CH and [(dpp-BIAN)Zn(μ-I)]2 (2) potassium hydride yield the binuclear complexes [(dpp-BIAN)Zn(μ-C≡CPh)]2 (3) [(dpp-BIAN)Zn(μ-H)]2 (4), respectively (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene). Complex 3 is also obtained by thermal dehydrogenation [dpp-BIAN(H)]Zn(C≡CPh) (5), which in turn can be prepared reacting ZnI2 equimolar amounts [dpp-BIAN(H)]Na PhC≡CNa. paramagnetic compounds 4 have been characterized ESR...