88544-61-0Relevant academic research and scientific papers
Targeting synthetic analogues of the metallo-sulfur active sites of nickel enzymes capable of important catalysis
Smith, Matt C.,Barclay, J. Elaine,Davies, Sian C.,Hughes, David L.,Evans, David J.
, p. 4147 - 4151 (2007/10/03)
The nickel containing enzymes NiFe-hydrogenase, carbon monoxide dehydrogenase and acetyl-CoA synthase are able to catalyse environmentally, and potentially industrially, important reactions: hydrogen uptake; carbon dioxide/carbon monoxide interconversion; and incorporation of carbon monoxide to form acetyl-CoA, respectively. Progress toward the synthesis of nickel-iron complexes with structural features related to the active sites of these enzymes are described, together with the synthesis, properties and crystal structure of the first methylated-nickel-iron diheterometallic complex, [{Fe(NS3)(NO)-S} Ni(CH3)(dppe)] (NS3 = N(CH2CH2S)33-), relevant to a proposed mechanistic intermediate in the acetyl-CoA synthase mechanism.
Reactions of Dialkylnickel(II) Complexes NiR2L2 with Alkyl (or Aryl) Halides, R'COY (Y=Cl, Br, OPh, OCOPh), and CS2
Yamamoto, Takakazu,Kohara, Teiji,Osakada, Kohtaro,Yamamoto, Akio
, p. 2147 - 2153 (2007/10/02)
Reactions of Ni(CH3)2(bpy) (1), Ni(C2H5)2(bpy) (2) (bpy=2,2'-bipyridine), trans-Ni(CH3)2(triethylphosphine)2 (3), Ni(CH3)2(1,2-bis(diphenylphosphino)ethane) (4), and Ni(CH3)2(1,3-bis(diphenylphosphino)propane) (5) with alkyl or aryl halides, R'COY (Y=Cl, Br, OC6H5, OCOC6H5), and CS2 have been investigated.The reactions of NiR2L2 with alkyl or aryl halides are classified into three types of reactions by their reaction products: Type A: NiR2L2 + R'X ->NiX(R')L2 + R-R, Type B: NiR2L2 + R'X -> alkane (RH) + olefin (R'(-H)), and Type C: NiR2L2 + R'X -> NiR(X)L2 + R-R'.Complexes 1 and 2 undergo mainly Type A reaction.Complex 3 gives Type A reaction product on treatment with C6H5Br, but it gives Type B reaction product on treatment with C2H5Br.On the other hand, 4 undergoes Type C reaction on interaction with C6H5Cl.The reactions with R'COY (Y=Cl, Br, OPh, OCOPh) are classiffed into two types of reactions by their reaction products: Type D: NiR2L2 + R'COY -> NiY(R)L2 + RCOR' and Type E: NiR2L2 + R'COY -> NiY(R')L2 + RCOR.Complexes 1-3 undergo mainly Type D reaction, whereas complexes 4 and 5 mainly Type E reaction.The diffrence in the reaction route is discussed on the basis of presence or absence of vacant coordination site for attack by R'COY.The reaction of 4 with CS2 affords Ni(CS2)(1,2-bis(diphenylphoshino)ethane) with evolution of a reductive elimination product, ethane, whereas the reaction of 3 with CS2 gives a 1:1 adduct of 3 and CS2.
