313705-80-5

Upstream product

• 7650-89-7 tribenzylphosphine 
• 1295-35-8 bis(1,5-cyclooctadiene)nickel ⁽⁰⁾ 
• 160593-79-3 C₆Cl₅(P(C₂H₅)2) 
• 6782-81-6 perchlororophenyl(diphenyl) phosphine 

Downstream Products

• 135395-96-9 NiClH(P(CH₂C₆H₅)3)2 
• 135396-06-4 (ethene)bis(tribenzylphosphine)nickel⁽⁰⁾ 
• 135395-96-9 trans-chlorohydridobis(tribenzylphosphine)nickel(II) 
• 1594112-87-4 trans-bis(tribenzylphosphine)(2-methylphenyl)nickel(II) chloride 

Relevant academic research and scientific papers

NICKEL PRE-CATALYSTS AND RELATED COMPOSITIONS AND METHODS

Described herein are nickel pre-catalysts and related compositions and methods. The nickel pre-catalysts may be activated to form catalysts which may be utilized in organic reactions.

A broadly applicable strategy for entry into homogeneous nickel(0) catalysts from air-stable nickel(II) complexes

A series of air-stable nickel complexes of the form L2Ni(aryl) X (L = monodentate phosphine, X = Cl, Br) and LNi(aryl)X (L = bis-phosphine) have been synthesized and are presented as a library of precatalysts suitable for a wide variety of nickel-catalyzed transformations. These complexes are easily synthesized from low-cost NiCl2·6H2O or NiBr 2·3H2O and the desired ligand followed by addition of 1 equiv of Grignard reagent. A selection of these complexes were characterized by single-crystal X-ray diffraction, and an analysis of their structural features is provided. A case study of their use as precatalysts for the nickel-catalyzed carbonyl-ene reaction is presented, showing superior reactivity in comparison to reactions using Ni(cod)2. Furthermore, as the precatalysts are all stable to air, no glovebox or inert-atmosphere techniques are required to make use of these complexes for nickel-catalyzed reactions.

Preparation of Four-membered Phosphonickelocycles. Unusual Facile Stabilization of Five-co-ordinate Complexes

Three different types of organometallic compounds (R = Ph 1 or Et 1'), (R = Ph 2 or Et 2') and (R = Ph 3 or Et 3') have been obtained from 1 equivalent of PR2(C6Cl5) (R = Ph or Et), (cod = cis,cis-cycloocta-1,5-diene), and L = PMe2Ph a, PEt3 b, P(CH2Ph)3 c or PPh3 d.Complexes 2 evolve in solution, either to 1 and , or to 3 by breaking of the Ni-P bond of the four-membered ring by free phosphine.The selective preparation of compounds 1 or 3 can be achieved by performing the oxidative-addition reaction in the absence or with 2 equivalents of L respectively.When 1 equivalent of a diphosphine was used in the oxidative-addition reaction a mononuclear five-co-ordinate complex was obtained, 4 .However, dppm (Ph2PCH2PPh2) acts as a monodentate ligand to give the five-co-ordinate compound .Complexes 2, 2' show preferentially a cis geometry, 1' is trans, and 3, 3' have the L ligands in trans position.Insertion of CO or alkynes into the Ni-C bond was not observed.Compounds 1 and 1' in the presence of neutral ligands L = CO or PR3 (PR3 = PMe2Ph a or PEt3 b) gave five-co-ordinate complexes without cleavage of the Ni-P bond of the ring.Stabilization of the four-membered ring is achieved when two bidentate ligands are present or in the five-co-ordinate compound .Two bidentate ligands are also needed to stabilize the formation of five-co-ordinate complexes.The molecular structures of complexes 1', 3b, and were determined by single-crystal X-ray diffraction.