15793-01-8

Basic information

• Product Name: Ni(CO)2{1,2-bis(diphenylphosphino)ethane}
• Synonyms: Ni(CO)2{1,2-bis(diphenylphosphino)ethane}
• CAS NO: 15793-01-8
• Molecular Weight: 513.135
• Mol File: 15793-01-8.mol

Chemical Properties

• CAS DataBase Reference: Ni(CO)2{1,2-bis(diphenylphosphino)ethane}(CAS DataBase Reference)
• NIST Chemistry Reference: Ni(CO)2{1,2-bis(diphenylphosphino)ethane}(15793-01-8)
• EPA Substance Registry System: Ni(CO)2{1,2-bis(diphenylphosphino)ethane}(15793-01-8)

Safety Data

• Hazardous Substances Data: 15793-01-8(Hazardous Substances Data)

Upstream product

• 115981-40-3 methyl(1,1,1,3,3,3-hexafluoro-2-propoxo){1,2-bis(diphenylphosphino)ethane}nickel 
• 14647-21-3 dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) 
• 15628-25-8 Ni⁽⁰⁾(1,2-bis(diphenylphosphino)ethane)2 
• 201230-82-2 carbon monoxide 
• 1295-35-8 bis(1,5-cyclooctadiene)nickel ⁽⁰⁾ 
• 4100-80-5 2-methylsuccinic anhydride 
• 13007-90-4 bis(triphenylphosphine)nickel⁽⁰⁾ dicarbonyl 
• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 
• 22891-72-1 Pentafluorphenylthioacetat 
• 1174330-25-6 (1,2-bis(diphenylphosphino)ethane)Ni(Me)(pentafluorothiophenolate) 
• 934-87-2 S-phenyl thioacetate 
• 14878-28-5 sodium tetracarbonyl cobaltate 
• 14647-23-5 1,2-bis(diphenylphosphino)ethane nickel(II) chloride 
• 81097-97-4 (1,2-bis(phenylphosphino)ethane)(dithiooxalato-S,S')nickel(II) 

Downstream Products

• 15628-25-8 Ni⁽⁰⁾(1,2-bis(diphenylphosphino)ethane)2 
• 116888-32-5 {μ-(diphos)NiS2}Fe2(CO)6 

Relevant articles and documents

Zerovalent Nickel Compounds Supported by 1,2-Bis(diphenylphosphino)benzene: Synthesis, Structures, and Catalytic Properties

Zerovalent nickel compounds which feature 1,2-bis(diphenylphosphino)benzene (dppbz) were obtained via the reactivity of dppbz towards Ni(PMe3)4, which affords sequentially (dppbz)Ni(PMe3)2 and Ni(dppbz)2. Furthermore, the carbonyl derivatives (dppbz)Ni(PMe3)(CO) and (dppbz)Ni(CO)2 may be obtained via the reaction of CO with (dppbz)Ni(PMe3)2. Other methods for the synthesis of these carbonyl compounds include (i) the formation of (dppbz)Ni(CO)2 by the reaction of Ni(PPh3)2(CO)2 with dppbz and (ii) the formation of (dppbz)Ni(PMe3)(CO) by the reaction of (dppbz)Ni(CO)2 with PMe3. Comparison of the ν(CO) IR spectroscopic data for (dppbz)Ni(CO)2 with other (diphosphine)Ni(CO)2 compounds provides a means to evaluate the electronic nature of dppbz. Specifically, comparison with (dppe)Ni(CO)2 indicates that the o-phenylene linker creates a slightly less electron donating ligand than does an ethylene linker. The steric impact of the dppbz ligand in relation to other diphosphine ligands has also been evaluated in terms of its buried volume (%Vbur) and steric maps. The nickel center of (dppbz)Ni(PMe3)2 may be protonated by formic acid at room temperature to afford [(dppbz)Ni(PMe3)2H]+, but at elevated temperatures, effects catalytic release of H2 from formic acid. Analogous studies with Ni(dppbz)2 and Ni(PMe3)4 indicate that the ability to protonate the nickel centers in these compounds increases in the sequence Ni(dppbz)2 3)2 3)4; correspondingly, the pKa values of the protonated derivatives increase in the sequence [Ni(dppbz)2H]+ 3)2H]+ 3)4H]+. (dppbz)Ni(PMe3)2 and Ni(PMe3)4 also serve as catalysts for the formation of alkoxysilanes by (i) hydrosilylation of PhCHO by PhSiH3 and Ph2SiH2 and (ii) dehydrocoupling of PhCH2OH with PhSiH3 and Ph2SiH2.

Synthetic analogs for evaluating the influence of N-H...S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase

A series of square planar methylnickel(II) complexes, (dppe)Ni(Me)(SAr) (dppe = 1,2-bis(diphenylphosphino)ethane); 2. Ar = phenyl; 3. Ar = pentafluorophenyl; 4. Ar = o-pivaloylaminophenyl; 5. Ar = p-pivaloylaminophenyl; (depe)Ni(Me)(SAr), (depe = 1,2-bis(diethylphosphino)ethane); 7. Ar = phenyl; 8. Ar = pentafluorophenyl; 9. Ar = o-pivaloylaminophenyl; 10. Ar = p-pivaloylaminophenyl), were synthesized via the reaction of (dppe)NiMe 2 (1) and (depe)NiMe2 (6) with either the corresponding thiol or disulfide. These complexes were characterized by various spectroscopic methods including 31P NMR, 1H NMR, 13C NMR and infrared spectroscopies and in most cases by X-ray diffraction analyses. Solid state and solution measurements establish that 4 and 9 contain intramolecular N-H...S bonds. Carbonylation of the complexes 2-4, 7-10 leads to (dRpe)Ni(CO)2 and MeC(O)SAr via the intermediacy of the acylnickel adducts, (dRpe)Ni(C(O)Me)(SAr), detected at low temperature by 31P NMR spectroscopy. Consistent with experimental observations, density functional theory results reveal that the intramolecular hydrogen bond in 9 stabilizes the acylnickel adduct compared with its non-hydrogen-bonded adduct, 10. Oxidative addition of MeC(O)SC6F5 to (dRpe)Ni(COD) followed by spontaneous decarbonylation proceeds in variable yields generating 3 and 8.

Studies of structural effects on the half-wave potentials of mononuclear and dinuclear nickel(II) diphosphine/dithiolate complexes

Two series of mononuclear Ni(II) complexes of the formula (PNP)Ni(dithiolate) where PNP = R2PCH2N(CH 3)CH2-PR2, R = Et and Ph, have been synthesized containing dithiolate ligands that vary from five- to seven-membered chelate rings. Two series of dinuclear Ni(II) complexes of the formula {[(diphosphine)Ni]2(dithiolate)}(X)2 (X = BF4 or PF6) have been synthesized in which the chelate ring size of the dithiolate and diphosphine ligands have been systematically varied. The structures of the alkylated mononuclear complex, [(PNPEt)Ni(SC 2H4SMe)]OTf, and the dinuclear complex, [(dppeNi) 2(SC3H6S)](BF4)2, have been determined by X-ray diffraction studies. The complexes have been studied by cyclic voltammetry to determine how the half-wave potentials of the Ni(II/I) couples vary with chelate ring size of the ligands. For the mononuclear complexes, this potential becomes more positive as the natural bite angle of the dithiolate ligand increases. However, the potentials of the Ni(II/I) couples of the dinuclear complexes do not show a dependence on the chelate ring size of the ligands. Other aspects of the reduction chemistry of these complexes have been explored.

Reactivity of Nickel(II) Diphosphine Complexes towards Alkoxides: a New Route to the Synthesis of Nickel(0) Compounds through Nickel(II) Alkoxides

Reaction of with NaOR (R = Me, Et or i-Pr) under a dinitrogen atmosphere afforded , Ni(OR)2 and aldehyde (or acetone when R = Pri) in 1:1:1 ratio, showing the peculiar reducing effect of alkoxide promoted by the chelating property of the phosphorus ligand.The reaction of NaOMe with afforded mainly when carried out in the absence of free diphosphine, and in the presence of free diphosphine.The reaction always yields the nickel(0) species when it is carried out under a carbon monoxide atmosphere.The intermediate formation of unstable alkoxo(diphosphine)nickel(II) complexes has been demonstrated by recording the 31P NMR spectra of the reactiong solutions at low temperature; in the case of the reaction of with NaOMe only, it was possible to isolate as a solid the complex, which has been fully characterized by analytical and spectroscopic (IR and 1H, 31P NMR) methods.A possible route by which nickel(0) complexes could be formed is discussed.

Preparation and properties of new methyl(alkoxo)- and methyl(thiolato)nickel and methyl(alkoxo)- and methyl(thiolato)palladium complexes. CO and CS2 insertion into the alkoxo-palladium bond

Reactions of fluorinated alcohols (HOCH(CF3)2, HOCH2CF3, and HOCH(CF3)C6H5) or aromatic thiols (HSC6H5 and HSC6H4-p-CH3) with dialkylnickel and -palladium complexes (NiMe2(bpy), NiEt2(bpy) (bpy = 2,2′-bipyridine), NiMe2(dpe), and PdMe2(dpe) (dpe = 1,2-bis(diphenylphosphino)ethane)) give the corresponding monoalkyl complexes with an alkoxo or a thiolato ligand (NiMe(OR)(bpy), NiEt(OR)(bpy), MMe(OR)(dpe), and MMe(SAr)(dpe) (M = Ni, Pd; R = CH(CF3)2, CH2CF3, CH(CF3)C6H5)). These complexes have been characterized by elemental analysis and NMR (1H, 31P{1H}, 19F, and 13C{1H}) spectroscopy. The methyl(alkoxo)nickel(II) and -palladium(II) complexes thus obtained react with carbon monoxide at normal pressure to give carboxylic esters in high yields. Reaction of carbon monoxide with NiMe(SAr)(dpe) (Ar = C6H5, C6H4-p-CH3) also gives the corresponding carbothioic esters in good yields, while PdMe(SPh)(dpe) is unreactive with carbon monoxide under similar conditions. The 31P{1H} and 13C{1H} NMR spectra of the reaction mixture of PdMe(OCH(CF3)2)(dpe) with an equimolar amount of 13CO at -60°C show the formation of PdMe (13COOCH(CF3)2)(dpe) produced through insertion of the carbon monoxide into the Pd-O bond. When the reaction temperature is raised to -20°C, this alkoxycarbonyl complex undergoes reductive elimination to give 1,1,1,3,3,3-hexafluoro-2-propyl acetate. The reaction is accompanied by simultaneous decarbonylation of the alkoxycarbonyl ligand to regenerate PdMe(OCH(CF3)2)(dpe). The reaction of PdMe(OCH(CF3)Ph)(dpe) with carbon disulfide gives an isolable palladium complex, PdMe(SCSOCH(CF3)Ph)(dpe), formed by insertion of CS2 into the Pd-O bond, while PdMe(SPh)(dpe) is unreactive with CS2.

Syntheses of photoactive complexes. Electronic spectra, electrochemistry, and SCF-Xα-DV calculations for bis(phosphine)palladium oxalate and dithiooxalate complexes. Crystal and molecular structures of (dithiooxalato-S,S′)bis(trimethylphosphine)palladium(II) and (1,1-dithiooxalato-S,S′)bis(μ 3-sulfido)-2,2,3,3-tetrakis(trimethylphosphine)-triangulo- tripalladium(II)

The compounds M(S2C2O2)L2 (M = Ni, Pd, Pt; L = P(CH3)3 (PMe3) or L2 = [P(C6H5)2CH2]2 (dppe), [P(C2H5)2CH2]2 (depe)) were prepared from the reaction between K2S2C2O2 and MCl2L2 (M = Ni, Pd, Pt; L = depe, dppe), except for NiCl2(PMe3)2, which was prepared from NiCl2(1,2-dimethoxyethane), K2S2C2O2, and PMe3. In all complexes the dithiooxalate ligand chelates through both sulfur atoms as evidenced by vC-O =1632-1640 cm-1 for the uncomplexed carbonyl groups in the solution IR spectra. Crystals of Pd(S2C2O2)(PMe3)2 belong to the space group Pbca with a = 13.479 (2) ?, b = 12.488 (2) ?, c = 17.542 (2) ?, Z = 8, and V = 2952.7 (7) ?3. Solution of the structure by direct methods led to final values of RF = 2.63 and RwF = 3.23 with 137 least-squares parameters for 2159 unique reflections with Fo > 5σ(Fo). The structure confirmed the square-planar structure about Pd with Pd-P = 2.294 (1) and 2.307 (1) ? and Pd-S = 2.324 (1) and 2.344 (1) ?. All dithiooxalate complexes were photoactive and liberated carbonyl sulfide and products derived from ML2 on photolysis. Thermolysis of Pd(S2C2O2)(PMe3)2 in DMF produced crystals of Pd3(μ3-S)2(S2C2O 2)(PMe3)4 on cooling that belong to the space group P21 with a = 9.580 (2) ?, b = 11.578 (2) ?, c = 13.400 (4) ?, β = 96.93 (2)°, Z = 2, and V = 1475.4 (4) ?3. Solution of the structure by direct methods led to final values of RF = 2.50 and RwF = 2.82 with 245 least-squares parameters for 2523 unique reflections with Fo > 5σ(Fo). The molecular structure consists of a triangle of palladium atoms with Pd(1)-Pd(2) = 3.174 (1) ?, Pd(1)-Pd(3) = 3.038 (1) ?, and Pd(2)-Pd(3) = 3.141 (1) ? capped above and below the plane by sulfurs Pd(1)-S(1) = 2.364 (2) ?, Pd(1)-S(2) = 2.374 (2) ?, Pd(2)-S(1) = 2.356 (2) ?, Pd(2)-S(2) = 2.353 (2) ?, Pd(3)-S(1) = 2.333 (2) ?, and Pd(3)-S(2) = 2.339(2) ?. The coordination geometry, including the capping sulfides, about each palladium is pseudo square planar with Pd(1) and Pd(2) each binding two PMe3 ligands and Pd(3) binding to a dithiooxalate-S,S′ ligand. SCF-Xα-DV calculations for the model complexes Pd(C2O4)(PH3)2 and Pd(S2C2O2)(PH3)2 show a similar orbital energy scheme. The lowest energy and presumably photoactive electronic transitions are to empty C2O42- and S2C2O22- π* orbitals rather than to a ligand to metal charge-transfer transition. Several of the dithiooxalate complexes prepared showed chemically reversible reductions at -1.5 to -1.6 V in CH3CN vs. Ag/AgCl, while all analogous oxalate complexes showed irreversible reductions at -1.5 to -2.1 V.

Preparation of Ni- or Pt-Containing Cyclic Esters by Oxidative Addition of Cyclic Carboxylic Anhydrides and Their Properties

Metal containing cyclic ester complexes, L (L=1,2-bis(diphenylphosphino)ethane (dpe) or 2,2'-bipyridine (bpy); R1, R2=H or CH3) and Ln )L=tricyclohexylphosphine (PCy3) or dpe; n=1 or 2), have been prepared by oxidative addition of cyclic carboxylic anhydrides to zero-valent metal complexes.These complexes have been characterized by elemental analysis and spectroscopies (IR as well as 1H-, 13C1H>-, and 31P1H>-NMR) and chemical rectivities.Rate of the oxidative addition of succinic anhydride to Ni(bpy)(cod) (cod=1,5-cyclooctadiene) is expressed by a second order rate equation, R=k, and temperature dependence of k gives the activation energy of 68 kJ mol-1.The reaction of methylsuccinic anhydride with Ni(cod)2 in the presence of tertiary phosphine or bpy affords two isomers, Ln and Ln, corresponding to two modes of C-O bond cleavage in methylsuccininc anhydride promoted by Ni; dependence of the ratio between the two isomers on the kind of ligand added and reaction conditions has been examined.

REACTIONS OF NiX2(dppe) (X = Cl, Br) WITH Na. SYNTHESIS AND CRYSTAL STRUCTURE OF Co2(μ-CO)2(CO)4(dppe) (dppe = Ph2PCH2CH2PPh2)

The reaction of Na with NiX2(dppe) (X=Cl, Br; dppe=1,2-bis(diphenylphosphino)ethane) in THF or toluene at -30 to 0 deg C produces mainly Ni(CO)2(dppe) and Co2(CO)6(dppe).The structure of this latter complex, determined by an X-ray analysis, can be regarded as derived from that of Co2(CO)8 by substitution of two terminal CO groups on one cobalt atom by the chelating dppe ligand.This structure could not have been predicted unambiguously solely on the basis of the interpretation of the infrared data.Crystals of Co2(μ-CO)2(CO)4(dppe) are monoclinic, space group P21/a, with Z=4, in a unit cell of dimensions a 21.117(13), b 17.012(10), c 8.436(6) Angstroem, β 93.76(5)o.The structure was solved by Patterson and Fourier methods and refined by full-matrix least-squares to R=0.053 for 1549 independent observed reflections.

Insertion of Carbon Monoxide into Nickel-Alkyl Bonds of Monoalkyl- and Dialkylnickel(II) Complexes, NiR(Y)L2 and NiR2L2. Preparation of Ni(COR)(Y)L2 from NiR(Y)L2 and Selective Formation of Ketone, Diketone, and Aldehyde from NiR2L2

Reactions of monoalkylnickel(II) complexes, NiR(Y)L2 (R=CH3, C2H5; Y=Cl, suc(succinimido), pht(phthalimido), OC6H4-p-CN; L=1/2 bpy (2,2'-bipyridine), PEt3 (triethylphosphine)), with CO afford monoacylnickel(II) complexes, Ni(COR)(Y)L2, which are characterized by elemental analysis and spectroscopies (IR and NMR).Reactions of the acylnickel(II) complexes with alcohols and aniline give the corresponding esters and amides, respectively.Exposure of Ni(COR)(Y)L2 to dry air leads to oxidation of RCO to a RCOO ligand giving a complex formulated as NI(OCOR)(Y)L2.Reactions of dimethylnickel(II) complexes, Ni(CH3)2L2 (L=1/2 bpy, PEt3, 1/2dpe (1,2-bis(diphenylphosphino)ethane, 1/2 dpp (1,3-bis(diphenylphosphino)propane), with carbon monoxide afford acetone and/or 2,3-butanedione in medium to high yields, the acetone/2,3-butanedione ratio varying with the ligand L, reaction temperature, and additives such as maleic anhydride and triphenylphosphine.Generally the acetone/2,3-butanedione ratio decreases with increase in thermal stabilities of Ni(CH3)2L2.Ni(C2H5)2(bpy) and Ni(n-C3H7)2(bpy) give 3-pentanone and 4-heptanone, respectively, on treating them with CO, whereas Ni(C2H5)2(dpe) produces C2H5CHO and C2H4.