Author Topic: Catalytic hydrogenation at STP with Ni(OAc)2-NaBH4  (Read 2092 times)

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Rhodium

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Catalytic hydrogenation at STP with Ni(OAc)2-NaBH4
« on: November 17, 2002, 06:04:00 PM »
The addition of sodium borohydride to an aqueous solution of Nickel(II)Acetate forms a precipitate of Nickel Boride (Ni2B, P-1 Nickel) which is at least as active as Raney Nickel for catalytic hydrogenation at 1 atm.

Catalytic Hydrogenation. V. The Reaction of Sodium Borohydride with Aqueous Nickel Salts.
P-1 Nickel Boride, a Convenient, Highly Active Nickel Hydrogenation Catalyst

Charles Allan Brown

J. Org. Chem. 56, 1900-1904 (1970)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/nickel.boride.cat-hyd-1atm.pdf)

Abstract
The reaction of sodium borohydride with aqueous solutions of nickel salts immediately produces a finely divided black precipitate. This material (P-1 nickel) is a highly active catalyst for atmospheric pressure hydrogenations, more active than Raney nickel. The hydrogenations of a variety of alkenes have been examined and all but the most hindered double bonds were reduced successfully. Certain dienes were reduced cleanly to single olefinic products. P-1 nickel has marked advantages over Raney nickel: it is not pyrophoric; it is readily prepared in situ; it is highly reproducible.

Barium

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Chem. Rev. 1986, 86, 763-780 Synthetically useful
« Reply #1 on: November 18, 2002, 03:07:00 PM »
Synthetically useful reactions with metal boride and aluminide catalysts

Chem. Rev. 86, 763-780 (1986)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/metal.boride.review.pdf)

This paper covers:
  • The making of P1- and P2-Ni2B
  • Hydrogenation of alkenes and alkynes
  • Reduction of arenes
  • Reduction of halides
  • Reduction of nitriles
  • Reduction of nitro compounds
  • Reduction of other nitrogenous functional groups such as oximes, amides, azoxy and nitroso
  • Deoxygenation reactions
  • Desulfurization

Rhodium

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Ref uploaded
« Reply #2 on: November 18, 2002, 07:29:00 PM »
Great! I have uploaded that one to my page and linked it from your post.

Barium

  • Guest
Hmm
« Reply #3 on: November 19, 2002, 05:24:00 PM »
I made som P1-Ni2B today just to see how active it was with a couple of my standard hydrogen donors.

with aq. sodium hypophosphite - very active at room temp
with MeOH/sodium hypophosphite - very active at room temp
with aq ammonium formate - active at room temp, very active at 50°C
with MeOH/ammonium formate - active at room temp, very active at 50°C

Now it is time to reduce something

Catalytic hydrogenation freak

Sunlight

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Nice Barium
« Reply #4 on: November 19, 2002, 10:59:00 PM »
Perhaps we could check it in the CTH reductive amination. Could you detail the preparation of the catalyst ?

Rhodium

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The preparation is available in the first post in ...
« Reply #5 on: November 20, 2002, 12:23:00 AM »
The preparation is available in the first post in this thread.

Sunlight

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Ok
« Reply #6 on: November 20, 2002, 03:01:00 PM »
So stupid... I have NiCl2, and there's something about bad effects of Cl and Na ions in the catalyst, it's a complication.

Aurelius

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Example
« Reply #7 on: November 21, 2002, 10:14:00 PM »
hey Barium, could you put a write up on your procedure for the reduction of (your choice) a compound including catalyst prep?

Rhodium

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He's done that before, just perform a search on ...
« Reply #8 on: November 21, 2002, 10:18:00 PM »
He's done that before, just perform a search on his name.

Aurelius

  • Guest
Thank
« Reply #9 on: November 22, 2002, 12:42:00 AM »
must have missed it