Synthesis and characterization of bis(phosphine)nickel(0) complexes containing nonsymmetrically substituted acetylenes

Bartik, Tamás; Happ, Berit; Iglewsky, Marek; Bandmann, Hans‐Jürgen; Boese, Roland; Heimbach, P.; Hoffmann, Thomas; Wenschuh, Eberhard

doi:10.1021/om00039a033

Cited by 44 publications

(18 citation statements)

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“…The J(PC) values are, in general, larger than those found in η 2 -alkynenickel() complexes. 8, 14 The IR band due to ν(C᎐ ᎐ ᎐ C) is observed at 1700 cm Ϫ1 , which is lower than that of the nickel analogue, in accord with the trend noted for other alkyne complexes of nickel() and platinum(). [15][16][17] Complex 5 is unaffected by MeOH, even at 50 ЊC, but addition of one mole equivalent of HCl in diethyl ether precipitates a colourless 1 : 1 adduct whose 31 P-{ 1 H} NMR spectrum in C 6 D 6 shows a broad signal at δ P 7.9 due to PPh 2 and two broad signals, with 195 Pt satellites, due to coordinated dcpe: a singlet at δ P 49.0 and a doublet at δ P 61.8.…”

Section: Resultssupporting

confidence: 77%

Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Bennett

Kwan

Rae

et al. 2001

J. Chem. Soc., Dalton Trans.

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Section: Resultssupporting

confidence: 77%

Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Bennett

Kwan

Rae

et al. 2001

J. Chem. Soc., Dalton Trans.

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“…These compounds were characterized by 1 H, 31 P, and 13 C{ 1 H} NMR spectroscopy. The 13 C{ 1 H} resonances of the alkyne carbons are similar to those reported for other bis(phosphine)nickel(0) acetylene complexes . Compound 1 was also characterized by X-ray crystallography (Figure ).…”

Section: Resultssupporting

confidence: 74%

Catalytic Carbon−Carbon and Carbon−Silicon Bond Activation and Functionalization by Nickel Complexes

1999

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The nickel alkyne complexes (dippe)Ni(Me3SiC⋮CSiMe3), 1, (dippe)Ni(Me3CC⋮CSiMe3), 2, and (dippe)Ni(MeC⋮CSiMe3), 3, were synthesized (dippe = bis(diisopropylphosphino)ethane) and characterized by 1H, 31P, and 13C{1H} NMR spectroscopy. Complex 1 was characterized by X-ray crystallography. Heating complex 1, 2, or 3 with excess biphenylene and alkyne results in the catalytic formation of several novel organic compounds, several of which have been characterized by X-ray crystallography. These reactions are proposed to proceed by a competition between β-silyl migration from an acetylene insertion intermediate and elimination of phenanthrene. Mechanistic schemes are presented for these reactions.

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“…Compound 5 was also characterized by 19 F NMR spectroscopy. The 13 C{ 1 H} resonances of the alkyne carbons are similar to those reported for other bis(phosphine)nickel(0) acetylene complexes . Compounds 1 , 2 , and 3 were also characterized by X-ray crystallography (Figures −3).…”

Section: Resultssupporting

confidence: 73%

“…The 13 C{ 1 H} resonances of the alkyne carbons are similar to those reported for other bis(phosphine)nickel(0) acetylene complexes. 6 Compounds 1, 2, and 3 were also characterized by X-ray crystallography (Figures 1-3). These compounds are distorted square-planar complexes (the alkyne is in the plane) with carbon-carbon triplebond distances similar to those reported for other nickel(0) alkyne complexes with electron-donating chelating phosphines.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Carbon−Carbon Bond Activation and Functionalization by Nickel Complexes

1999

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The nickel alkyne complexes (dippe)Ni(PhCtCPh), 1, (dippe)Ni(MeCtCMe), 2, (dippe)-Ni(MeO 2 CCtCCO 2 Me), 3, (dippe)Ni(CH 3 OCH 2 CtCCH 2 OCH 3 ), 4, and (dippe)Ni(CF 3 CtCCF 3 ), 5, were synthesized (dippe ) bis(diisopropylphosphino)ethane) and characterized by 1 H, 31 P, and 13 C{ 1 H} NMR spectroscopy. Complexes 1, 2, and 3 were characterized by X-ray crystallography. The thermolysis of complex 1 or 2 (120 °C) in the presence of excess biphenylene and excess alkyne results in very slow catalytic formation of the corresponding 9,10-disubstituted phenanthrene. However, addition of ∼6 mol % O 2 (based on the metal complex) to the reaction mixture results in an acceleration in catalysis at lower temperatures (∼70-80 °C). The thermolysis of complexes 3 or 4 with excess biphenylene and excess alkyne leads to the alkyne cyclotrimerization product as the major organic species formed in the reaction. Fluorenone was catalytically produced by heating (dippe)Ni(CO) 2 , biphenylene, and CO. Catalytic insertion of 2,6-xylylisocyanide into the strained C-C bond of biphenylene was also achieved by heating (dippe)Ni(2,6-xylylisocyanide) 2 , excess biphenylene, and 2,6xylylisocyanide. Mechanistic schemes are proposed for these reactions.

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Synthesis and characterization of bis(phosphine)nickel(0) complexes containing nonsymmetrically substituted acetylenes

Cited by 44 publications

References 0 publications

Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine

Catalytic Carbon−Carbon and Carbon−Silicon Bond Activation and Functionalization by Nickel Complexes

Catalytic Carbon−Carbon Bond Activation and Functionalization by Nickel Complexes

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