56792-69-9

Usage

Uses

Substrate or catalyst for numerous organometallic transformations, including the Nicholas reaction, the Pauson– Khand reaction, alkyne cyclotrimerization, and alkyne hydrosilylation Precursor for the atomic layer deposition of Cobalt containing thin films

Synthetic route

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + 2,2-dimethyl-3-butyne (917-92-0) → (3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9)

Conditions	Yield
With ionic liquid-modified graphene oxide material at 30℃; for 10h; Inert atmosphere;	88.7%
In diethyl ether at 20℃; for 3h; Inert atmosphere;	71%
In diethyl ether at 20℃; for 3h; Inert atmosphere;	71%

dicobalt octacarbonyl + 2,2-dimethyl-3-butyne (917-92-0) → (3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9)

Conditions	Yield
In hexane N2-atmosphere; equimolar amts., room temp., few min; chromy. (SiO2, hexane);

2,2-dimethyl-3-butyne (917-92-0) + dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) → (3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9)

Conditions	Yield
In hexane (N2 or Ar); using Schlenk techniques; treatment of 1.0 equiv. of Co2(CO)8 with (t-Bu)CCH in hexane at room temp.;

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + carbon monoxide (201230-82-2) → Co2(CO)7(C4HO2C(CH3)3)

Conditions	Yield
In hexane High Pressure; dry, deoxygenated solvent and gases; dissolution in hexane, charging into autoclave (Ar atmosphere), changing of Ar for CO, pressurization (p(CO) = 27 MPa), heating (90+/-5°C, 12 h, CO supplementation each hour), cooling (room temp., 40 min); filtration, concn., chromy. (silica gel, hexane); elem. anal.;	92%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + (-)-(1S,4S,6R,8R)-4-diphenylphosphino-11,11-dimethyl-5-oxa-3-thiatricyclo[6.2.1.0(1,6)]undecane borane complex → [Co2(μ-Me3CCCH)(CO)4(μ-C23H27OPS)]

Conditions	Yield
With DABCO In toluene byproducts: CO; charging of Co2(CO)6(HCC(t-Bu)), Me2C9H11SOPPh2BH3 (1 equiv.), DABCO (1.5 equiv.) and toluene in a Shlenk flask under N2, heating at 60°Cfor 20 h and then at 80°C under CO atmosphere for 66 h; monitoring by TLC, removal of solvent in vac., flash chromy. on SiO2, NMR analysis, as mixt. of two diastereoisomers in 2:1 ratio;	90%

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + (3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → C(CH3)3CH2CCo3(CO)9

Conditions	Yield
With hydrogen In benzene reaction of complexes in benzene with 3-4 atm of H2 at 65°C for 5 days in a sealed vessel; filtration, evapn., chromy. (silica, hexane), recrystn. (methanol); elem. anal.;	80%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + (+)-(1S,4S,6R,8R)-4-diphenylphosphino-4,11,11-trimethyl-5-oxa-3-thiatricyclo[6.2.1.0(1,6)]undecane borane complex → [Co2(μ-Me3CCCH)(CO)4(μ-C24H29OPS)]

Conditions	Yield
With DABCO In toluene byproducts: CO; charging of Co2(CO)6(HCCCMe3), Me3C9H10SOPPh2BH3 (1 equiv.), DABCO (1.5 equiv.) and toluene in a Shlenk flask under N2, heating t 65°C for 18 h; filtration through a pad of silica (hexane/AcORt), NMR analysis, as mixt. of two diastereoisomers in 20:1 ratio;	80%

hydrido(tricarbonyl)(cyclopentadienyl)molybdenum (12176-06-6) + (3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → Co2(CO)6Mo(C5H5)(CO)2(CCH2C4H9) (87226-35-5)

Conditions	Yield
In benzene 45°C, 20 h; elem. anal.;	75%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + phosphorous acid trimethyl ester (121-45-9) → H((CH3)3C)C2Co2(CO)5(P(OCH3)3) (84896-06-0)

Conditions	Yield
In acetonitrile byproducts: CO; Electrolysis; inert gas; -0,82 V; 5 min; solvent was removed; chromatographed;	74%
In hexane byproducts: CO; inert gas; 3 h; boiling hexane; solvent was removed; chromatographed;	69%
With benzophenone ketyl In tetrahydrofuran byproducts: CO; inert gas; a small amount benzophenone ketyl was added to a solution ofthe Co-complex and the phosphite; 293 K; solvent was removed; chromatographed;	61%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + diethyl-phenyl-phosphine (1605-53-4) → Co2(CO)5(diethylphenylphosphine)(HCC-t-Bu) (63395-25-5)

Conditions	Yield
In n-heptane N2-atmosphere; addn. of 2 equiv. of phosphine to Co-complex, stirring (30°C, 4 h); filtration, concn. (vac.), chromy. (SiO2, petroleum ether, dark red band), evapn.; elem. anal.;	60%

2,3-bis(diphenylphosphino)maleic anhydride (51501-24-7) + (3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → Co2(CO)4(2,3-bis(diphenylphosphino)maleic anhydride)(μ-t-BuC.tplbond.CH) (179921-68-7, 179921-70-1)

Conditions	Yield
With Me3NO In tetrahydrofuran addn. of 2 equiv. Me3NO to equimolar mixt. of Co-complex and anhydride, stirring for 1 h; solvent removal, chromy. (-78°C, SiO2, CH2Cl2/petroleum ether=3:1), recrystn. (CH2Cl2/pentane); elem. anal.;	57%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → H((CH3)3C)C2Co2(CO)5(P(C6H5)3) (84896-07-1)

Conditions	Yield
With triphenyl phosphine In hexane inert gas; 3 h; boiling hexane; solvent was removed; chromatographed;	54%
With benzophenone ketyl; triphenyl phosphine In tetrahydrofuran byproducts: CO; inert gas; a small amount benzophenone ketyl was added to a solution ofthe Co-complex and the phosphine; 293 K; solvent was removed; chromatographed;	42%
With triphenyl phosphine In acetonitrile byproducts: CO; Electrolysis; inert gas; -0,82 V; 5 min; solvent was removed; chromatographed;	17%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + 2,2-dimethyl-3-butyne (917-92-0) → Co2(CO)4C18H30

Conditions	Yield
In petroleum ether	30%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) + (S)-4-tert-butyl-2-[2-(diphenylphosphino)phenyl]-4,5-dihydro-1,3-oxazol (148461-16-9) → [[2-[(4S)-4-(tert-bytyl)(1,3-oxazolin-2-yl)]phenyl]diphenylphosphine]Co2((CH3)3CCCH)(carbonyl)5 + [[2-[(4S)-4-(tert-bytyl)(1,3-oxazolin-2-yl)]phenyl]diphenylphosphine]Co2((CH3)3CCCH)(carbonyl)5

Conditions	Yield
In toluene under N2; to a soln. of the Co complex in toluene was added the ligand, the mixt. was stirred at 70°C for 3 h; chromy. (SiO2);	A 21% B 16%

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → C(CH3)3CH2CCo3(CO)9

Conditions	Yield
In not given by heating, in acidic medium;
In not given by heating, in acidic medium;

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → Co2(CO)4(μ-η(2):η(2):η(1):η(1)-t-BuC=C(H)PPh2C=C(PPh2)C(O)OC(O))

Conditions	Yield
Multi-step reaction with 3 steps 1: Me3NO / tetrahydrofuran 2: 1,2-dichloro-ethane 3: 1,2-dichloro-ethane View Scheme

(3,3-dimethyl-1-butynyl)hexacarbonyl dicobalt (56792-69-9) → Co2(CO)4(2,3-bis(diphenylphosphino)maleic anhydride)(μ-HC.tplbond.C-t-Bu) (179921-68-7, 179921-70-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: Me3NO / tetrahydrofuran 2: 1,2-dichloro-ethane View Scheme

Upstream product

• 75-24-1 trimethylaluminum 
• 15226-74-1 dicobalt octacarbonyl 
• 917-92-0 3,3-Dimethylbut-1-yne 
• 15226-74-1 dicobalt octacarbonyl 

Downstream Products

• 63395-25-5 Co₂(CO)5(diethylphenylphosphine)(HCC-t-Bu) 
• 179921-68-7 Co2(CO)4(2,3-bis(diphenylphosphino)maleic anhydride)(μ-HC.tplbond.C-t-Bu) 
• 179921-68-7 Co2(CO)4(2,3-bis(diphenylphosphino)maleic anhydride)(μ-t-BuC.tplbond.CH) 
• 84896-08-2 H((CH₃)3C)C₂Co₂(CO)5(P(C₆H₁₁)3) 
• 84896-07-1 H((CH₃)3C)C₂Co₂(CO)5(P(C₆H₅)3) 

Relevant academic research and scientific papers

On the reactivity of acetylenes coordinated to cobalt. Part 81: carbonylation of acetylenes with bulky substituents

Acetylenes (R1C2R2, R1=H, R2=n-Pr,i-Pr,t-Bu, neo-Pent) with equimolar Co2(CO)8 or the corresponding (R1C2R2Co2(CO)6 (1) com

Design of new hemilabile (P,S) ligands for the highly diastereoselective coordination to alkyne dicobalt complexes: Application to the asymmetric intermolecular Pauson-Khand reaction

Here we synthesized a new generation of hemilabile P,S ligands designed for diastereoselective coordination to terminal alkyne-hexacarbonyldicobalt complexes. The camphor-derived CamPHOS (2) and MeCamPHOS (12) ligands were obtained in 68% and 59% yield in their borane-protected form starting from readily available 1,3-oxathiane 4. Thermally induced coordination to dicobalt-hexacarbonyl-alkyne (HCCR, R = Ph, But, SiMe3, C(CH3)2OH) complexes was studied. MeCamPHOS (12) provided an unprecedented diastereoselectivity on coordination to terminal complexes (up to 90% de). The solid state structure of a coordinated CamPHOS ligand with [Co2(μ-ButSO2C)2(CO)6] was determined and confirms the preference to coordinate the bimetallic cluster in a bridged manner. The resulting adducts were submitted to the intermolecular Pauson-Khand cyclization. Remarkably, CamPHOS and MeCamPHOS provided Pauson-Khand products of opposite absolute configurations. This behavior could be explained on the basis that 2 and 11 ligands lead to pseudoenantiomeric tetracarbonyl complexes, as confirmed by circular dichroism analysis. Introduction of a CH3- group on the carbon bridge between P and S increased CamPHOS selectivity dramatically from 33% to 90% de of the opposed sign with an overall destabilizing effect of 2.15 kcal/mol for 7b.

REACTIONS OF (PROPARGYL)DICOBALT HEXACARBONYL CATIONS WITH METHYLMETALS

The reactions of several methyl-metallic compounds, (CH3)MLn with the cobalt complexes CCR1R2)Co2(CO)6>+BF4- (I) and (HCCCR1R2OAc)Co2(CO)6 (VIII) have been examined and assessed as a synthetic method for methyl/propargyl coupling.No methyl transfer was observed in the reactions of the cationic complexes I with CH3MgI, (CH3)2Cd, (CH3)2Gg, (CH3)4Si, (CH3)4Sn or (CH3)3SiSi(CH3)3 but rather reductively coupled products, (HCCCR1R2-Cr1R2CCH)2 (III), and (HCCCHR1R2)Co2(CO)6 (V) were obtained in low yields.Modest yields (5-30percent) of methylation products (HCCCR1R2CH3)Co2(CO)6 (II) were produced from I and (C5H5)Fe(CO)2CH3 or (CH3)3Al, accompanied by varying amounts of III.The most efficient route to the methylated derivatives II (25-90percent yields) combines the complexed propargyl acetates VIII with (CH3)3Al under unusually mild conditions (CH2Cl2, -78 deg C).

METHOD OF SELECTIVELY FORMING COBALT METAL LAYER BY USING COBALT COMPOUND, AND METHOD OF FABRICATING SEMICONDUCTOR DEVICE BY USING COBALT COMPOUND

A method of selectively forming a cobalt metal layer includes supplying a cobalt compound represented by Chemical Formula (1) onto a substrate that includes a wiring line of a late transition metal and an isolation film adjacent thereto, and supplying a reducing gas to selectively form a cobalt metal layer on the wiring line,

Preparation method of (3,3-dimethyl-1-butyne)dicobalt hexacarbonyl

The invention relates to the field of fine chemical engineering, and concretely relates to a preparation method of (3,3-dimethyl-1-butyne)dicobalt hexacarbonyl. The method comprises the following steps: adding a cobalt carbonyl reagent and 1500-2000 parts of a hydrocarbon solvent into a reactor under the protection of a nitrogen atmosphere, then controlling the temperature to be 0-30 DEG C, then slowly adding 0.1-0.5 part of an ionic liquid modified graphene oxide material and 20-30 parts of tert-butylacetylene into the system, and then carrying out a stirring reaction under the protection ofthe nitrogen atmosphere for 1-10 h after the materials are added; and performing filtration after the completion of the reaction, distilling the obtained filtrate to remove volatile components to obtain crude (3,3-dimethyl-1-butyne)dicobalt hexacarbonyl, and then purifying the crude (3,3-dimethyl-1-butyne)dicobalt hexacarbonyl to obtain the (3,3-dimethyl-1-butyne)dicobalt hexacarbonyl. The preparation method has the advantages of high operability, few reaction byproducts, high yield and large-scale industrialization prospect.

COBALT PRECURSOR AND METHODS FOR MANUFACTURE USING THE SAME

The inventive concept relates to a cobalt precursor, a method for manufacturing a cobalt-containing layer using the same, and a method for manufacturing a semiconductor device using the same. More particularly, the cobalt precursor of the inventive concept includes at least one compound selected from the group consisting of a compound of Formula 1 and a compound of Formula 2.