Correction: NHC-Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes.

Correction for 'NHC-Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes' by Adimulam Harinath , , 2023, https://doi.org/10.1039/d3ob00453h.

NHC-Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes.

An -heterocyclic carbene-zinc alkyl complex [ImZn(CHCH)] (Im = imidazol-2-ylidene and Dipp = 2,6-diisopropylphenyl) acts as a catalyst in the cross-dehydrogenative coupling (CDC) of a wide range of primary and secondary amines and hydrosilanes to yield a substantial quantity of the corresponding aminosilanes with good chemoselectivity at room temperature. A broad substrate scope was observed during the zinc-catalyzed CDC reaction. Two zinc complexes, [{ImZn(-NHPh)(NHPh)}] (Mes = mesityl) (3) and [{ImZn(CHCH)(-H)}] (4), were isolated and structurally characterized as intermediates through controlled reactions to ascertain the CDC mechanism.

Reactivity of Silylene with Gallium- and Boron Trihalide at Reductive Conditions Resulting in Unforeseen Products.

Herein, we report a one-pot reaction of gallium and boron halides with potassium graphite in the presence of benzamidinate stabilized silylene LSi-R, (L=PhC(N Bu) ). The reaction of LSiCl with an equivalent amount of GaI in the presence of KC leads to the direct substitution of one chloride group by gallium diiodide simultaneously additional coordination of silylene resulted in L(Cl)Si→GaI -Si(L)→GaI (1). In compound 1, the structure comprises two differently coordinated gallium atoms where one gallium presents between two silylenes and the other gallium is only coordinated by one silylene.

A highly efficient Ti-catalyst for the deoxygenative reduction of esters under ambient conditions: experimental and mechanistic insights from DFT studies.

In this paper, we report the synthesis of dianionic amidophosphineborane-supported titanium chloride [{PhP(BH)N}CHTiCl] (1) and Ti alkyl complex [{PhP(BH)N}CHTi(CHSiMe)] (2) using a salt metathesis reaction. Ti complex 1 was obtained by the reaction of the bis-borane ligand [{PhP(BH)NH}CH] and TiCl in toluene followed by the addition of 2 equivalents of [LiN(SiMe)] at ambient temperature. Ti bis-alkyl complex 2 was isolated from the reaction of complex 1 with 2.

Alkaline Earth Metal-Mediated Highly Iso-selective Ring-Opening Polymerization of rac-Lactide.

Alkaline earth (Ae) metal complexes of the aminophosphine borane ligand are highly active and iso-selective catalysts for the ring-opening polymerization (ROP) of rac-lactide (LA). The polymerization reactions are well controlled and produce polylactides with molecular weights that are precise and narrowly distributed. Kinetic studies reveal that the ROP of rac-LA catalyzed by all Ae metal complexes had a first-order dependency on LA concentration as well as catalyst concentration.

Highly Chemoselective Hydroboration of Alkynes and Nitriles Catalyzed by Group 4 Metal Amidophosphine-Borane Complexes.

We report a series of titanium and zirconium complexes supported by dianionic amidophosphine-borane ligands, synthesized by amine elimination and salt metathesis reactions. The Ti complex [{PhP(BH)N}CHTi(NMe)] () was obtained by the reaction between tetrakis-(dimethylamido)titanium(IV) and the protic aminophosphine-borane ligand [{PhP(BH)NH}CH] () at ambient temperature. Both the heteroleptic zirconium complexes-[η-(CH)Zr{PhP(BH)N}CH] () and [[{PhP(BH)N}CH]ZrCl] ()-and the homoleptic zirconium complex [[{PhP(BH)N}CH]Zr] () were obtained in good yield by the salt metathesis reaction of either zirconocene dichloride [η-(CH)ZrCl] or zirconium tetrachloride with the dilithium salt of the ligand [{PhP(BH)NLi}CH] (), which was prepared in situ.

Facile reduction of carboxylic acids to primary alcohols under catalyst-free and solvent-free conditions.

We report the development of a facile protocol for the deoxygenative hydroboration of aliphatic and aryl carboxylic acids to afford corresponding primary alcohols under solvent-free and catalyst-free conditions. The reaction proceeds under ambient temperature exhibits good tolerance towards various functional groups and generates quantitative yields. The plausible mechanism involves the formation of Lewis acid-base adducts as well as the liberation of hydrogen gas.

Highly Active Dinuclear Titanium(IV) Complexes for the Catalytic Formation of a Carbon-Heteroatom Bond.

A series of mononuclear titanium(IV) complexes with the general composition κ-[R{NHPhP(X)}Ti(NMe)] [R = CH, X = Se (3b); R = trans-CH, X = S (4a), Se (4b)] and [{κ-N(PPhSe)}Ti(NMe)] (6b) and two dinuclear titanium(IV) complexes, [CH{(NPhPS)(N)}Ti(NMe)] (3c) and [{κ-N(PPhSe)}Ti(NMe)] (6c), are reported. Dinuclear titanium(IV) complex 6c acts as an efficient catalyst for the chemoselective addition of an E-H bond (E = N, O, S, P, C) to heterocumulenes under mild conditions. The catalytic addition of aliphatic and aromatic amines, alcohol, thiol, phosphine oxide, and acetylene to the carbodiimides afforded the corresponding hydroelemented products in high yield at mild conditions with a broader substrate scope.

Alkali metal complexes as efficient catalysts for hydroboration and cyanosilylation of carbonyl compounds.

We report here reactions between the N-adamantyliminopyrolyl ligand 2-(AdN[double bond, length as m-dash]CH)-C4H3NH (L-H) and alkali metal hexamethyldisilazides [MN(SiMe3)2] (M = Li, Na and K) to afford the dimeric [{2-(AdN[double bond, length as m-dash]CH)-C4H3NLi(THF)}2] (1), [{2-(AdN[double bond, length as m-dash]CH)-C4H3N}{Na(THF)1.5}2] (2) and polymeric [{2-(AdN[double bond, length as m-dash]CH)-C4H3NK(THF)}n] (3) complexes at ambient temperature. A one-pot reaction between L-H, [KN(SiMe3)2] and alkaline earth metal diiodide (AeI2) in a 2 : 2 : 1 molar ratio, which resulted in the formation of a heteroleptic Ae metal complex [κ2-{2-(AdN[double bond, length as m-dash]CH)-C4H3N}2Ae(THF)2] [Ae = Mg (4), Ca (5)], is also reported.

Ring Opening Polymerization and Copolymerization of Cyclic Esters Catalyzed by Group 2 Metal Complexes Supported by Functionalized P-N Ligands.

We report the preparation of alkali and alkaline earth (Ae) metal complexes supported by 2-picolylamino-diphenylphosphane chalcogenide [(PhP(=E)NHCH(CHN)] [E = S (1-H); Se (2-H)] ligands. The treatment of the protic ligand, 1-H or 2-H, with alkali metal hexamethyldisilazides at room temperature afforded the corresponding alkali metal salts [M(THF)(PhP(=E)NCH(CHN)] [M = Li, E = S (3a), Se (3b)] and [{M(THF) (PhP(=E)NCH(CHN)}] [M = Na, E = S (4a), Se (4b); M = K, E = Se (5b)] in good yield. The homoleptic Ae metal complexes [κ-(PhP(=Se)NCH(CHN)Mg(THF)] (6b) and [κ-{(PhP(=Se)NCH(CHN)}M(THF) ] (M = Ca (7b), Sr (8b), Ba (9b)] were synthesized by the one-pot reaction of 2-H with [KN(SiMe)] and MI in a 2:2:1 molar ratio at room temperature.

Highly Active and Iso-Selective Catalysts for the Ring-Opening Polymerization of Cyclic Esters using Group 2 Metal Initiators.

A series of alkali and alkaline earth (Ae) metal complexes bearing 1,2-phenylene(bis-diphenylphosphinothioic/selenoic amine) [{Ph P(E)NH} C H ] (E=S (1-H2); Se (2-H2) ligands are reported. Alkali metal complexes [{Ph P(S)N} C H ]Na(THF) (3 a) [{Ph P(Se)N} C H ]Na(THF) (3 b), and [{Ph P(Se)N} C H ]K(THF) (4 b) were obtained in good yield by treating protic ligands 1-H2 or 2-H2 with metal hexamethyldisilazides [MN(SiMe ) ] (M=Na or K) at ambient temperature. The Ae metal complexes formulated as [{Ph P(E)N} C H ]M(THF) [E=S, M=Ca (5 a), Sr (6 a), Ba (7 a); E=Se, M=Ca (5 b), Sr (6 b), Ba (7 b)] can be synthesized by using two routes.

Synthesis, structure and reactivity study of magnesium amidinato complexes derived from carbodiimides and N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligands.

We report an amidinato ligand-supported series of magnesium complexes obtained from the insertion of a magnesium-carbon bond into a carbon-nitrogen double bond of different carbodiimides and α-diimine ligands. The magnesium complexes [Mg(CH2Ph){CyN[double bond, length as m-dash]C(CH2Ph)NCy}]2 (), [Mg(CH2Ph){(i)PrN[double bond, length as m-dash]C(CH2Ph)N(i)Pr}]2 () and the homoleptic [Mg{(t)BuN[double bond, length as m-dash]C(CH2Ph)N(t)Bu}2] () (Cy = cyclohexyl, (i)Pr = isopropyl, (t)Bu = tert-butyl) were prepared by the reaction of dibenzyl magnesium [Mg(CH2Ph)2(Et2O)2] with the respective carbodiimides either in 1 : 1 or 1 : 2 molar ratio in toluene. The analogous reaction of [Mg(CH2Ph)2(Et2O)2] with the N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (Dipp2DAD) ligand afforded the corresponding homoleptic magnesium complex [Mg{DippN[double bond, length as m-dash]C(CH2Ph)CH2NDipp}2] () (Dipp = 2,6 diisopropylphenyl) in good yield.

Titanium and zirconium complexes of the N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligand: syntheses, structures and uses in catalytic hydrosilylation reactions.

We report here a number of dianionic 1,4-diaza-1,3-butadiene complexes of titanium and zirconium synthesised by a salt metathesis reaction. The reaction of either CpTiCl3 or Cp2TiCl2 with the dilithium salt of N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene [; abbreviated (Dipp)2DADLi2] afforded the mono-cyclopentadienyl titanium complex [η(5)-CpTi((Dipp)2DAD)Cl] () bearing a dianionic ene-diamide ligand, while the analogous reaction of zirconocene dichloride (Cp2ZrCl2) with the dilithium salt gave the bis-cyclopentadienyl zirconium complex [Cp2Zr{(Dipp)2DAD}] (). The metal dichloride complexes [Ti((Dipp)2DAD)Cl2] () and [{(Dipp)2DADZrCl(μ-Cl)}2(κ(3)-Cl)(Li)(OEt2)2] () were obtained by the reaction of and anhydrous metal tetrachloride in a 1 : 1 molar ratio in diethyl ether at room temperature.

Bis(phosphinoselenoic amides) as versatile chelating ligands for alkaline earth metal (Mg, Ca, Sr and Ba) complexes: syntheses, structure and ε-caprolactone polymerisation.

We report here a series of heavier alkaline earth metal complexes with N,N'-(ethane-1,2-diyl)bis(P,P-diphenylphosphinoselenoic amide) using two synthetic routes. In the first route, the heavier alkaline earth metal bis(trimethylsilyl)amides [M{N(SiMe3)2}2(THF)n] (M = Ca, Sr, Ba), when treated with phosphinoselenoic amine [Ph2P(Se)NHCH2CH2NHPPh2(Se)] (1), afforded the corresponding alkaline earth metal complexes of the composition [(THF)3M{Ph2P(Se)NCH2CH2NPPh2(Se)}] [M = Ca (2), Sr (3), Ba (4)]. The metal complexes 2-4 were also obtained from a one-pot reaction, where potassium phosphinoselenoic amide was generated in situ by the reaction of compound 1 and [KN(SiMe3)2], followed by the addition of the respective metal diiodides in THF at room temperature.