88440-32-8

Upstream product

• 88510-50-3 [(((C₆H₅)2PCH₂CH₂)3N)Ni(CO)]⁽¹⁺⁾*B(C₆H₅)4^(1-)=[(((C₆H₅)2PCH₂CH₂)3N)Ni(CO)]B(C₆H₅)4 
• 141-52-6 sodium ethanolate 
• 95099-93-7 (N(CH₂CH₂P(C₆H₅)2)3)Ni(CO₂C₂H₅)⁽¹⁺⁾*B(C₆H₅)4^(1-)=[(N(CH₂CH₂P(C₆H₅)2)3)Ni(CO₂C₂H₅)]B(C₆H₅)4 
• 52633-73-5 (tris(2-diphenylphosphinoethyl)amine)nickel⁽⁰⁾ 

Downstream Products

• 95099-93-7 (N(CH₂CH₂P(C₆H₅)2)3)Ni(CO₂C₂H₅)⁽¹⁺⁾*B(C₆H₅)4^(1-)=[(N(CH₂CH₂P(C₆H₅)2)3)Ni(CO₂C₂H₅)]B(C₆H₅)4 

Relevant academic research and scientific papers

REACTIVITY OF Ni TOWARD CS2, SCNPh, AND COS. STRUCTURE OF THE η2-S,C-BONDED PHOSPHONIODITHIOMETHYL ESTER COMPLEX

Reaction of (np3)Ni (np3 = tris(2-diphenylphosphinoethyl)amine) with CS2, SCNPh, or COS affords (np3)Ni(η2-CS2) (5), (np3)Ni(η2-SCNPh) (9), and (np3)NiCO (12), respectively.Methylation of 5 by MeOSO2F, followed by NaBPh4 addition, leads to (6) through intramolecular attack by a phosphorus atom of np3 on a η2-dithiomethyl ester group formed in situ.The structure of 6 has been determined from counter diffraction data.Crystal data are: a 28.148(16), b 14.448(8), c 33.922(17) Angstroem, β 112.11(4) deg, monoclinic, space group C2/c, Z = 8.The structure was solved by the heavy-atom method and refined by full-matrix least-squares.Refinements converged at the conventional R factor value of 0.095 for 1989 reflections having I >= 3?(I).

Solid-gas reactions of molecular organometallic complexes. Detection of a metastable intermediate in the carbonylation of a nickel(0) complex

The reaction of the trigonal pyramidal Ni(0) complex [Ni(NP3)] (1) with CO in tetrahydrofuran (THF) solution has been re-investigated [NP3 = N(CH2CH2PPh2)3]. Depending on the experimental conditions, the reaction gives either the monocarbonyl [Ni(η3-NP3-P,P′,P″)(CO)] (2) or the dicarbonyl [Ni(η2-NP3-P,P′)(CO)2] (3a). Both products exhibit a distorted tetrahedral coordination geometry; in the monocarbonyl complex, the NP3 ligand uses the three phosphorus atoms to bind the metal center, whereas it uses two phosphorus only in 3a. Compounds 2 and 3a have been characterized by IR and 31P and 13C NMR spectroscopies in both the solid state and solution. Compound 3a is thermally stable in the solid state under inert atmosphere even at high temperature whereas, in ambient temperature solutions, it readily converts to 2 via CO elimination. The solid-gas reaction between crystals of 1 and CO (1 atm) at room temperature gives a mixture of 2 and of a new species 3b, which has the same stoichiometry as 3a but exhibits a different 31P CPMAS spectrum. On dissolution in THF saturated with CO, 3b converts to 3a whereas, under inert atmosphere, it dissolves to give initially 3a and later 2 and CO. In light of in situ DRIFT and 31P CPMAS spectroscopies, 3b is suggested to be an ensemble of metastable species in which a phosphine arm from NP3, although unfastened, is located close to the metal center as a consequence of the constraining environment of the crystal lattice. The proximity of the free phosphine arm to nickel makes solid 3b capable of losing one CO ligand, thus converting to 2. Unlike in solution, the latter compound undergoes thermal dissociation of CO in the solid state to generate the starting complex 1.

Reactivity of formaldehyde and acetaldehyde toward [N(CH2CH2PPh2)3]Ni and [N(CH2CH2PPh2)3]CoH

The Ni(0) complex (np3)Ni [np3 = tris(2-(diphenylphosphino)ethyl)amine] reacts with formaldehyde to give the paramagnetic Ni(I) formyl complex (np3)Ni(CHO), which decomposes to the diamagnetic Ni(0) carbonyl (np3)Ni(CO). Formaldehyde reacts with the Co(I) hydride (np3)CoH or with the methyl complex (np3)Co(CH3) to give the hydrido carbonyl compound (np3)Co(CO)H. When the latter reactions are carried out in the presence of NaBPh4, the cationic carbonyl [(np3)Co(CO)]BPh4 is formed. Acetaldehyde and propionaldehyde react with (np3)CoH yielding the corresponding paramagnetic η1-acyl complexes (np3)Co(COCH3) and (np3)Co(COC2H5). The reactivity of the acetyl derivative toward nucleophiles and electrophiles is investigated. Nucleophiles displace the acetyl ligand to give the corresponding complexes (np3)Co(Nu), whereas electrophiles remove the acetyl ligand to give the [(np3)Co]+ moiety. Possible reaction mechanisms are suggested on the basis of chemical and theoretical data.

SYNTHESIS AND REACTIVITY TOWARD REDUCING AGENTS OF THE ETHOXYCARBONYL COMPLEX BPh4 (np3 = tris(2-diphenylphosphinoethyl)amine)

The ethoxycarbonyl complex has been synthesized by ethoxide ion attack on (np3)Ni(CO) (3) or BPh4 (4).Compound 2 reacts with LiHBEt3, NaBH4, MeMgI, NaC10H8, or MeLi to give t