28796-12-5

Upstream product

• 57307-01-4 (P(C₆H₁₁)3)2Ni*CO₂ = (P(C₆H₁₁)3)2Ni(CO₂) 
• 108-98-5 thiophenol 
• 82384-39-2 trans-NiH(succinimido)((C₆H₁₁)3P)2 
• 201230-82-2 carbon monoxide 
• 613-90-1 benzoyl cyanide 
• 36568-49-7 Ni(P(C6H11-cyclo)3)2 
• 2622-14-2 tricyclohexylphosphine 
• 380499-25-2 Ni(PCy₃)2(cod) 
• 1333166-43-0 (S)-5-benzyl-1,3-dioxolane-2,4-dione 
• 1295-35-8 bis(1,5-cyclooctadiene)nickel⁽⁰⁾ 
• 455-32-3 benzoyl fluoride 
• 41685-59-0 ethene-bis(tricyclohexylphosphane)-nickel(0) 
• 1295-35-8 bis(1,5-cyclooctadiene)nickel ⁽⁰⁾ 
• 692-45-5 vinyl formate 

Downstream Products

• 53323-82-3 ((CH₃)2C(CH₂OP(OCH₂)2C(CH₃)2)2)Ni(P(C₆H₁₁-cyclo)3)2 

Relevant academic research and scientific papers

Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides

This Article describes the development of a base-free, nickel-catalyzed decarbonylative coupling of carboxylic acid fluorides with diboron reagents to selectively afford aryl boronate ester products. Detailed studies were conducted to assess the relative rates of direct transmetalation between aryl boronate esters and diboron reagents and a bisphosphine nickel(aryl)(fluoride) intermediate. These investigations revealed that diboron reagents undergo transmetalation with this Ni(aryl)(fluoride) intermediate at rates significantly faster than their aryl boronate ester congeners. Furthermore, the reactivity of both boron reagents toward transmetalation is enhanced with increasing electrophilicity of the boron center. These mechanistic insights were leveraged to develop a catalytic decarbonylative borylation of acid fluorides that proved applicable to a variety of (hetero)aryl carboxylic acid fluorides as well as diverse diboron reagents. The acid fluorides can be generated in situ directly from carboxylic acids. Furthermore, the mechanistic studies directed the identification of various air-stable Ni pre-catalysts for this transformation.

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides

Poly(α-hydroxy acids) are important biodegradable polymers with wide applications. Attempts to synthesize them from O-carboxyanhydrides with pendant functional groups by various methods, including methods involving organocatalysts or organometallics, have been plagued by uncontrolled polymerization, including epimerization for some monomers, which hampers the preparation of stereoregular high-molecular-weight polymers. Herein we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, allowing for the synthesis of isotactic polyesters with expected molecular weights (>140 kDa) and narrow molecular weight distributions (Mw/Mn a low temperature (?20 °C) and photoredox Ni/Ir catalysis synergistically accelerates ring-opening and decarboxylation of the monomer for chain propagation while avoiding the formation of the undesired Ni-carbonyl complex.

Nickel-Catalyzed Decarbonylative Coupling of Aryl Esters and Arylboronic Acids

A variety of functionalized biaryls can be accessed by coupling aryl and heteroaryl esters with boronic acids in Suzuki-Miyaura-type decarbonylative cross-coupling catalyzed by an affordable catalyst system composed of Ni(cod)2 and PCy3. The methodology is tolerant of a variety of functional groups and presents an attractive alternative to the use of palladium catalysis currently used in industry to acquire such bis(hetero)aryls, but also reveals challenges associated with nickel catalysis of esters in cross-coupling chemistry.

Synthetic, structural, and thermochemical studies of N-heterocyclic carbene (NHC) and tertiary phosphine ligands in the [(L)2Ni(CO)2] (L = PR3, NHC) system

Two new dicarbonyl N-heterocyclic carbene nickel(0) complexes of the type (NHC)2Ni(CO)2 (NHC = ICy, [N,N′- bis(cyclohexylimidazol)-2-ylidene (2), IMes [N,N′-bis(2,4,6- trimethylphenyl)imidazol)-2-ylidene] (3)) have been prepared by a substitution reaction of (NHC)Ni(CO)2 (NHC = ItBu [N,N′-bis(tert- butylimidazol)-2-ylidene], IAd [N,N′-bis(1-adamantylimidazol)-2-ylidene]) and 2 equivalents of ICy or IMes. Single-crystal X-ray analyses confirmed the monomeric 18-electron compositions of [(ICy)2Ni(CO)2] (2) and [(IMeS)2Ni(CO)2] (3). The greater electron-donating properties of the NHC ligands compared to tertiary phosphines are also demonstrated through calorimetric studies and enabled the determination of average bond dissociation enthalpies for Ni-L (L = NHC and tertiary phosphine).

Bioinorganic chemistry of nickel and carbon dioxide: An Ni complex behaving as a model system for carbon monoxide dehydrogenase enzyme

In this paper we report the results of our studies on Ni complexes, the chemistry of which is relevant to the carbon monoxide dehydrogenase (CODH) enzyme of acetogenic bacteria. A single Ni system is able to promote both the reduction of carbon dioxide to carbon monoxide and the subsequent coupling of bound CO with an olefin and a thio group to afford an organic thioester, mimicking the enzyme activity.

Reduction of Co-ordinated Carbon Dioxide to Carbon Mo oxide via Protonation by Thiols and other Broensted Acids promoted by Ni-Systems: A Contribution to the Understanding of the Mode of Action of the Enzyme Carbon Monoxide Dehydrogenase

Carbon dioxide co-ordinated to Ni0 is easily reduced to bound carbon monoxide by R-SH (R=H, alkyl, benzyl, phenyl, and substituted phenyl) and other Broensted acids, providing a reasonable model for the Ni-containing enzyme carbon monoxide dehydrogenase.

Oxidative Addition of Esters of Formic Acid and β-Lactones to Ni(0)-Complexes Involving Cleavage of the C-O Bond

Reactions of esters of formic acid, HCOOR (R = C2H5, CH2C6H5), with Ni(0)-complexes (mixtures of bis(1,5-cyclooctadiene)nickel (Ni(cod)2) and tertiary phosphines (PR'3)), lead to decarbonylation of HCOOR to afford (Ni(CO)n(PR''3)4-n and ROH.Vinyl formate gives a mixture of CH3CHO, Ni(CO)n(PR'3)4-n, C2H4, and CO2 on interaction with the Ni(0)-complexes. β-Lactones liberate CO2 on treatment with the Ni(0)-complexes.Oxidative addition of the reactants to Ni involving cleavage of the C-O bond(s) accounts for the formation of the products.

PREPARATION OF SEVERAL NEW TRANSITION METAL HYDRIDO COMPLEXES OF A TYPE MH(Y)Ln (M=Ni, Pd, Pt; Y=IMIDO, ALKENYL CARBOXYLATO) AND ELIMINATION OF HY FROM THE COMPLEXES ON INTERACTION WITH ?-ACIDS

MH(succinimido) (PCy3)2 (M=Ni, Pd) and trans-PtH(OCOR) (PCy3)2 (R= -C(CH3)=CH2, -CH2CH=CH2) have been prepared by oxidative addition of succinimide or the corresponding acid to the zerovalent transition metal complexes.Treatment of the hydrido complexes with ?-acids such as CO and maleic anhydride causes elimination of succinimide or RCOOH.

CARBONYLATION OF CYANO(PHENYL)BISLIGAND-NICKEL(II) COMPLEXES AND RELATED REACTIONS OF BENZOYL CYANIDE WITH NICKEL(O) COMPLEXES

Carbonylation of the complexes Ni(CN)(C6H5)(P)2 (P=P(C2H5)3; P(cyclo-C6H11)3; 0.5(C2H5)2P-(CH2)4-P(C2H5)2) affords the acyl-derivatives Ni(CN)-(COC6H5)(P)n (n=1,2) which, in the presence of excess CO, undergo reductive elimination of C6H5COCN.It has been