Methylenecyclopropanes (MCPs) have emerged as versatile building blocks in synthetic chemistry because of their unique reactivity. However, metal-catalyzed hydrosilylation MCPs has met with very limited successes. In this paper, catalytic selective hydrosilylations some primary silanes using an ene-diamido lanthanum ate complex the catalyst were described. The reactions resulted formation silacyclopentanes and (E)-homoallylsilanes, respectively, depending on substituents MCPs. via a cascade...

Monomeric iminoalane: A donor-stabilized monomeric iminoalane was prepared by the reaction of 1 with an N-heterocyclic carbene (see scheme). The X-ray structure exhibits a very short AlN bond 1.705(4) Å, which suggests multiple-bond character. Treatment phenyl acetylene, aniline, and carbon monoxide resulted in addition reactions to formal AlN bond, thus indicating that multiple is highly reactive. Detailed facts importance specialist readers are published as "Supporting Information". Such...

Allenes are versatile synthons in organic synthesis and medicinal chemistry because of their diverse reactivities. Catalytic 1,4-hydrosilylation 1,3-enynes may present the straightforward strategy for silylallenes. However, transition-metal-catalyzed reaction has not been successful due to poor selectivity very limited substrate scopes. We report here efficient selective branched enabled by ene-diamido rare-earth ate catalysts using both alkyl aryl hydrosilanes, leading exclusive formation...

A new route from benzylic imines permits the synthesis of 1,2-borazaronaphthalenes in good yields. The reaction involves formation enamidyl dibromoborane, which undergoes base-promoted borylation nearby aromatic C-H bond. Electrophilic attack boron species onto arene is supported by slow arenes substituted with electron-withdrawing groups. resultant bromides can be easily lithium reagents to provide a range products. electronic properties these 1,2-borazaronaphthalene derivatives have been...

Rare-earth-catalyzed regioselective hydrosilylation of internal alkenes with an ene-diamido samarium alkyl as a precatalyst has been described. The complex LSmCH2SiMe3(THF)2 (2, L = DipNC(Me)C(Me)NDip, where Dip 2,6-iPr2C6H3) enabled highly aryl-substituted primary silanes, leading to the selective formation series secondary silanes in high yields.

Hydrosilylation of alkynes generally yield vinylsilanes, which are inert to the further hydrosilylation because steric effects. Reported here is first successful dihydrosilylation aryl- and silyl-substituted internal enabled by a rare-earth ate complex geminal bis- tris(silanes), respectively. The lanthanum bis(amido) supported an ene-diamido ligand proved be ideal catalyst for this unprecedented transformation, while same series yttrium samarium alkyl complexes exhibited poor activity...

The well-defined NHC-copper phosphides [(NHC)CuPPh2]3 (1, NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr); 2, N,N-di-tert-butylimidazol-2-ylidene (ItBu)) have been prepared by the reaction of simple copper halides with HPPh2 in presence N-heterocyclic carbenes (NHCs). Complexes 1 and 2 enabled catalytic double hydrophosphination alkyl aryl terminal alkynes to yield 1,2-diphosphinoethanes selectively good yields. On basis these results, most efficient pratical situ CuCl2/NHC...

Samarium methoxide incorporating the ene-diamido ligand L(DME)Sm(μ-OMe)2Sm(DME)L (1; L = [DipNC(Me)C(Me)NDip](2-), Dip 2,6-iPr2C6H3, and DME 1,2-dimethoxyethane) has been prepared structurally characterized. Complex 1 catalyzed syndiospecific polymerization of styrene upon activation with phenylsilane regioselective hydrosilylation styrenes nonactivated terminal alkenes. Unprecedented regioselectivity (>99.0%) for both types alkenes achieved formation Markovnikov anti-Markovnikov products in...

One-pot multiple borylation of phenylhydrazones to a series novel boron-nitrogen analogues benzopentalene by the cleavage C-H bonds with PhBBr2 mediated NEt3 has been established. The resulting BN benzopentalenes feature unique electronic structures and are luminescent both in solution solid state.

Silylalkenes are important synthetic intermediates to substituted alkenes and silicon materials can be directly obtained by the catalytic selective hydrosilylation of alkynes. In this Letter, α-syn-hydrosilylation both aryl- silyl-substituted internal alkynes is described with an ene-diamido rare-earth ate complex as a catalyst. The reaction resulted in formation trisubstituted silylalkenes, including geminal disilylalkenes. kinetic study DFT calculations disclosed crucial roles structure...

Most of the renewable energy sources have unstable supply and high volatility. With growing share in integrated system, it is more difficult to execute pre-dispatch regulation decision system. To address problem increased volatility study proposes optimize decision-making system’s control center by analyzing difference between day-ahead market clearing price declared electricity supply. The results show that node power much higher than ground's actual during period from 1:00 am 4:00 am....

The NHC-stabilized silicon–carbon mixed cumulene (Me3Si)2C═Si(IPr)═Si(IPr)═C(SiMe3)2 (3, IPr = 1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene) has been prepared by reaction of Ar(SiMe3)NK with the silene (Me3Si)2C═Si(SiMe3)Cl(IPr) (2) in toluene at low temperature via elimination trimethylsilyl and chloride groups from 2. X-ray crystal analysis 3 indicated formal C═Si═Si═C skeleton short Si–Si double bond distance 2.1896(10) Å. DFT calculations disclosed its zwitterionic character. Reaction...

A new strategy for the highly selective synthesis of tricyclo[2,2,0,02,5]hexasilanes R6Si6X2 (R = 2,4,6-Me3C6H2; X H, Cl) and a bridged tricyclic R6Si6 dianion starting from tetrachlorotrisilane RCl2SiSi(H)RSiCl2R (1) was described. Reduction 1 with lithium naphthalene afforded tricyclohexasilane R6Si6H2 (2), which halogenated to give dichloride R6Si6Cl2 (3). 3 four equivalents potassium graphite in presence 18-crown-6 first (5) paired [K(18-crown-6)]+2 counterions. The 5 could act as...

Reaction of the aluminum hydroxide LAl(OH)[C(Ph)CH(Ph)] (1, L = HC[(CMe)(NAr)](2), Ar 2,6-iPr(2)C(6)H(3)) with Y(CH(2)SiMe(3))(3)(THF)(2) yielded oxo-bridged heterobimetallic yttrium dialkyl complex LAl[C(Ph)CH(Ph)](μ-O)Y(CH(2)SiMe(3))(2)(THF)(2) (2). Alkane elimination reaction 2 2-(imino)pyrrole [NN]H ([NN]H 2-(ArN═CH)-5-tBuC(4)H(2)NH) afforded monoalkyl LAl[C(Ph)CH(Ph)] (μ-O)Y(CH(2)SiMe(3))[NN](THF)(2) (5). Alternatively, 5 can be prepared in high yield by 1 [NN]Y(CH(2)SiMe(3))(2)(THF)(2)...

Abstract The catalytic hydrophosphination of imines represents the most straightforward and atom‐economical strategy for preparation α‐aminophosphines, which are useful as biologically active molecules ligands catalysis. first protocol rapid high‐yielding common enabled by an ene–diamido samarium methoxide catalyst was developed. reaction allowed efficient diastereoselective synthesis various bis(α‐amino)phosphines through double addition PhPH 2 to imines. has a relatively wide substrate...

Polycarbosilanes with SiH2 units in the main chain may undergo diverse reactions to access a family of functionalized polymers enhanced added values. However, preparation such has been hampered by uncontrollable side involving Si–H bonds under transition-metal-catalyzed conditions. We described here first selective bis-hydrosilylation dienes bis(hydrosilanes) enabled rare-earth-metal catalysts yield linear polycarbosilanes chain. The could halogenation, Si–O coupling, and hydrosilylation...

The highly regioselective synthesis of trans-1,2-disilylimines have been achieved by the bis-silylation nitriles with NHC-stabilized silylene NHC-Si(NArSiMe3)Cl (1; Ar = 2,6-iPr2C6H3, NHC 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene). involves migration SiMe3 group on nitrogen atom in to carbon nitrile functionality. 1,2-disilylimine products feature an silaimine moiety and could undergo nucleophilic attack phenyllithium reagents yield novel silaaziridines exocyclic Si═N double bond.

A four-coordinate yttrium dialkyl complex with a sterically demanding silaamidinate ligand exhibited high activity and excellent functional group tolerance for the catalysis of isocyanate cyclotrimerization.