Benz-amidinato dichlorosilane [PhC(N<italic>t</italic>Bu)₂SiHCl₂] has been reported to catalyze hydroboration of aldehydes at room temperature and aldimines under slightly harsh conditions.

Simple and readily accessible lithium compounds are found to be efficient single site catalysts for cyanosilylation hydroboration of a range aldehydes ketones under ambient conditions.

Ever increasing demand for green and sustainable chemical processes has set up a drive to replace transition metals with earth-abundant, nontoxic, environmentally benign alternatives. In this regard, the alkaline earth metal complexes have attracted significant attention. Herein, we used β-diketiminato ligand methyl-pyridine side arm synthesize magnesium (1) calcium (2) compounds. The constitutions of 1 2 been confirmed by single crystal X-ray studies, which show that atom in possesses...

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized the preparation PhC(NtBu)2Si{Si(SiMe3)3} (1) from PhC(NtBu)2SiHCl2 K{Si(SiMe3)3} in more than 90% yield. The highly deshielded 29Si NMR resonance (δ = 76.91 ppm) can be attributed to absence π-donating substituent. molecular structure 1 shows trigonal-planar geometry around SiII center SiII-SiIV bond length 2.4339(13) Å. A series reactions Me3NO, S, Se, and Te were performed. While siloxane...

A very simple and readily accessible lithium compound has been employed to catalyze the hydroboration of tertiary, secondary, primary amides corresponding amines.

The metal-catalyzed intermolecular C–H borylation of arenes is an extremely powerful functionalization methodology. However, to date it effectively restricted forming organo-boronate esters (Aryl–B(OR)2) with its application form other organoboranes rarely explored. Herein, we report a catalytic arene method using the commercial and inexpensive hydroborane 9-borabicyclo-[3.3.1]-nonane, (H–BBN)2. This process effective for mono- di-borylation range Aryl–BBN compounds either NacNacAl or...

In this study, sila[1]ferrocenophanes with sterically bulky groups such as tris(trimethylsilyl) or N‐heterocyclic iminato located at the bridging silicon atom were synthesized. The reactions of silicon‐bound chloride in Fe(η5‐C5H4)2SiCl2 (1) K[Si(SiMe3)3] and silylated imine resulted 2 3 silicon‐ nitrogen‐based substituents ansa bridge via elimination KCl Me3SiCl. Subsequently, we attempted reduction 1 using 2,3,5,6‐tetramethyl‐1,4‐bis(trimethylsilyl)‐1,4‐dihydropyrazine (popularly known...

This study demonstrates the first example of use a penta-coordinate Si(<sc>iv</sc>) hydride (PhC(N<italic>t</italic>Bu)₂SiH(CH₃)Cl) as catalyst for cyanosilylation variety aldehydes under mild conditions.

The hydroboration of alkenes and alkynes using easily accessible lithium compounds [2,6-di-tert-butyl phenolatelithium (1a) 1,1' dilithioferrocene (1b)] has been achieved with good yields, high functional group tolerance excellent chemoselectivity. Deuterium-labeling experiments confirm the cis-addition pinacolborane. methodology further extended to myrcene, which undergoes selective 4,3-hydroboration. DFT calculations provide insights into mechanism.

[(NacNac)Zn(DMT)][B(C6F5)4], 1, (NacNac = {(2,6- i Pr2H3C6)N(CH3)C}2CH), DMT N,N-dimethyl-4-toluidine), was synthesized via two routes starting from either (NacNac)ZnEt or (NacNac)ZnH. Complex 1 is an effective (pre)catalyst for the C-H borylation of (hetero)arenes using catecholborane (CatBH) with H2 only byproduct. The scope included weakly activated substrates such as 2-bromothiophene and benzothiophene. Computational studies elucidated a plausible reaction mechanism that has overall free...

The metal-catalyzed intermolecular C–H borylation of arenes is an extremely powerful functionalization methodology. However, to date it effectively restricted forming organo-boronate esters (Aryl–B(OR)2) with its application to...

The recently reported hypersilylsilylene PhC(NtBu)2SiSi(SiMe3)3 (1) reacts with BH3, 9-BBN, and PhBCl2 to yield the respective Lewis acid base adducts 2–4, respectively. Compound 4 undergoes isomerization form a ring expansion product 5. same silylene was found initially an adduct HBpin (6) subsequently isomerized 7 via rupture of B–H bond (7), where hydride bound carbon atom amidinate ligand Bpin unit attached silicon center. Surprisingly, reaction 1 HBcat results in PhC(NtBu)2Bcat (8)....

Abstract The isolation of unusual compounds with low‐valent main‐group elements would not have been possible without the development a series sterically demanding ligands bulky substituents. While early literature recognizes advent tris(trimethylsilyl)silyl (SiMe 3 ) Si‐group, also known as hypersilyl group, to stabilize species new coordination modes for main group elements, it has largely more recent studies that utilized this isolating stable elements. Such are only interesting from...

The recently published silylene with a tris(trimethylsilyl) group, PhC(NtBu)2SiSi(SiMe3)3 (1), was reacted the organic azides such as SiMe3N3 and AdN3 to form respective hypersilylsilaimines, PhC(NtBu)2Si(═NR)Si(SiMe3)3 2 (R = SiMe3) 3 Ad). B–H bond of HBpin or HBcat split across Si═N upon reaction 2, which generated 4 5, respectively. However, we could not obtain crystals 5 appropriate for X-ray diffraction. Subsequently, performed analogous reactions related silaimine...

Reduction of primary and secondary amides to amines without the need any catalyst has been developed.

The reaction of PhC(NtBu)2SiSi(SiMe3)3 (1) with Me3SiCH2Cl afforded an unsymmetrical sp2-sp3 disilene, 2, concomitant elimination Me3SiCl. analogous PhC(NtBu)2SiCl resulted in the oxidative addition C-Cl bond at Si(II) atom (3). reactions 2 sulfur and selenium led to compounds SiE (ES (4) Se (5)) double bonds. Tellurium reacted differently furnished a zwitterionic compound, 6.

Abstract Disilenes with differently coordinated silicon atoms are not known. Here, we have shown the high yield synthesis of a range disilenes ( 2 – 4 and 6 ) upon reaction hypersilyl silylene PhC(N t Bu) SiSi(SiMe 3 1 aliphatic chlorophosphines. The most striking characteristic these is presence two Si (one three‐coordinated, other four‐coordinated). analogous Ph PCl did afford desired disilene, but, surprisingly, led to first tetraphosphinosilane 8 ). DFT calculations were performed...

We have prepared amidinato-germylene (3) and -stannylene (4) with a tris(trimethylsilyl)silyl substituent subsequently substituted the hypersilyl moiety by reacting 3 chlorophosphines, which led to phosphino germylenes (5 6) concomitant liberation of (Me3Si)3SiCl. Exploiting fluoride affinity silicon atom, we pentafluoropyridyl germylene (7) (8) 4 C5F5N simultaneous elimination (Me3Si)3SiF. These are first examples aryl or stannylenes via C–F bond activation perfluoroarene. The reaction...

C−H metalation is the most efficient method to prepare aryl–zinc and –aluminum complexes that are highly useful nucleophiles. Virtually all C–H routes form Al or Zn organometallic reagents require stoichiometric, strong Brønsted bases with no base-catalyzed reactions reported, our knowledge. Herein we present a catalytic process aryl-zinc aryl-aluminum uses only simple amine (e.g., Et3N) in sub-stoichiometric quantity (10 mol%). Key this approach coupling an endergonic step using...

A truly green chemical process would avoid the use of an external catalyst, while still achieving high efficiency. This has been realized in very recent past for hydroboration, cyanosilylation, acetalization, and aza-Michael addition, among other reactions. The current combined computational experimental study unlocks secret to how this highly desirable outcome is accomplished: one reactants also acts as catalyst. Specifically, shown (i) important hydroboration reaction, with pinacolborane...

The activation of the <italic>para</italic> C–F bond C₅F₅N by IDipp led to functionalization all three carbon atoms imidazole ring. When is replaced with a C–H bond, activates other bonds leaving intact.

Abstract C−H metalation is the most efficient method to prepare aryl–zinc and –aluminium complexes that are ubiquitous nucleophiles. Virtually all routes form Al/Zn organometallics require stoichiometric, strong Brønsted bases with no base‐catalyzed reactions reported. Herein we present a catalytic in amine/ammonium salt (Et 3 N/[(Et N)H] + ) process aryl‐zinc aryl‐aluminium complexes. Key this approach coupling an endergonic step sufficiently exergonic dehydrocoupling between ammonium...

Abstract C−H metalation is the most efficient method to prepare aryl–zinc and –aluminium complexes that are ubiquitous nucleophiles. Virtually all routes form Al/Zn organometallics require stoichiometric, strong Brønsted bases with no base‐catalyzed reactions reported. Herein we present a catalytic in amine/ammonium salt (Et 3 N/[(Et N)H] + ) process aryl‐zinc aryl‐aluminium complexes. Key this approach coupling an endergonic step sufficiently exergonic dehydrocoupling between ammonium...

Abstract Disilenes with differently coordinated silicon atoms are not known. Here, we have shown the high yield synthesis of a range disilenes ( 2 – 4 and 6 ) upon reaction hypersilyl silylene PhC(N t Bu) SiSi(SiMe 3 1 aliphatic chlorophosphines. The most striking characteristic these is presence two Si (one three‐coordinated, other four‐coordinated). analogous Ph PCl did afford desired disilene, but, surprisingly, led to first tetraphosphinosilane 8 ). DFT calculations were performed...