- A convenient synthetic protocol to 1,2-bis(dialkylphosphino)-ethanes
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1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step.
- Doyle, Laurence R.,Heath, Alex,Low, Choon Heng,Ashley, Andrew E.
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supporting information
p. 603 - 608
(2014/05/20)
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- ETHYLENE TETRAMERIZATION CATALYST SYSTEMS AND METHOD FOR PREPARING 1-OCTENE USING THE SAME
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Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4).
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Page/Page column 12
(2010/06/16)
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- Process for the preparation of substituted aromatic compounds
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A process for the preparation of a substituted aromatic compound in which a chloroaromatic compound and an alkyl-, alkenyl- or aryl-boronic acid ester or anhydride are coupled in the presence of palladium and a lipophilic aliphatic phosphine comprising at least one branched aliphatic group or a lipophilic aliphatic Dis(phosphine). Preferred phosphines include triisopropyl, triisobutyl and tricyclohexylphosphine.
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- Oxidative Addition of Nickel(0) Complexes to Carbon-Carbon Bonds in Cyclobutadiene. The Question of the Interconvertibility of Cyclobutadiene-nickel(0) Complexes and the Nickelaring Systems
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Bis(triethylphosphine)(η4-tetraphenylcyclobutadiene)nickel (4) was synthesized by the reduction of (η4-tetraphenylcyclobutadiene)nickel(II)bromide (3) with t-butyllithium in the presence of Et3P, and its structure was determined by X-ray crystallography.Furthermore, its reactivity towards CO, CH3CO2H, PhCCPh, LiAlH4 and O2 were investigated. 1,1-Bis(triethylphosphine)-2,3,4,5-tetraphenylnickelole (14) was synthesized from (E,E)-1,4-dilithio-1,2,3,4-tetraphenyl-1,3-butadiene (15) and bis(triethylphosphine)nickel(II)bromide.Since the resulting crystals of the nickelole were not suitable for X-ray structure determination, the compound was characterized by elemental analyses, spectral data and carbonylation to yield tetraphenylcyclopentadienone (6).Analogous reductions of (η4-tetraphenylcyclobutadiene)nickel(II)bromide (3) in the presence of Ph3P or Ph2PCH2CH2PPh2, followed by carbonylation, led to 6 in 40percent yield, demonstrating that about half of the cyclobutadiene rings in 3 undergo cleavage upon reduction to give the nickelole.Reactions of the dilithium reagent 15 with NiBr2 complexed with Me2PCH2CH2PMe2, Ph3P or Et2PCH2CH2PEt2, led to the formation of thermolabile nickeloles, as demonstrated by carbonylation which yielded 6.Warming of the nickeloles and subsequent treatment with CH3CO2H led to the formation of 1,2,3,4,5,6,7,8-octaphenyl-1,3,5,7-octatetraene (8) and, in one case, octahenylcyclooctatetraene (5).The relevance of these findings to the mechanism of the Reppe nickel-catalyzed oligomerization of alkynes is discussed. - Key words: Insertion Reaction, Oxidative Addition, Cyclobutadiene-Nickel(0) Complexes, Nickelacyclopentadiene, Nickelole
- Eisch, John J.,Piotrowski, Andrzej M.,Aradi, Allen A.,Krueger, Carl,Romao, Maria J.
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p. 624 - 635
(2007/10/02)
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