Organometallic Chemistry OGOSHI Lab.


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AlMe3-Promoted Oxidative Cyclization of η2-Alkene and η2-Ketone on Nickel(0). Observation of Intermediate in Methyl Transfer Process

S. Ogoshi, M. Ueta, T. Arai, and H. Kurosawa
J. Am. Chem. Soc.2005, 127, 12810-12811.
AlMe3 can promote the oxidative cyclization of η2-alkene and η2-ketone on nickel(0) to give an intriguing nickel-aluminum dinuclear complex having a bridging Me group, which might be an intermediate for the nickel-catalyzed cycloisomerization of o-allylacetophenone or o-allylbenzophenone.

Direct Observation of Oxidative Cyclization of η2-Alkene and η2-Aldehyde on Ni(0) Center. Significant Acceleration by Addition of Me3SiOTf

S. Ogoshi, M.-a. Oka, and H. Kurosawa
J. Am. Chem. Soc. 2004, 126, 11802-11803.
5-Hexenal derivatives can coordinate to a nickel(0) center, affording a series of η2:η2-5-hexenalnickel complex.
The η2:η2-5-enal complex undergoes intramolecular oxidative cyclization to form an oxanickelacyclopentane, and addition of Me3SiOTf results in drastic acceleration of the cyclization reaction.

Dimerization of terminal alkynes catalyzed by a nickel complex having a bulky phosphine ligand

S. Ogoshi, M. Ueta, M.-a. Oka, and H. Kurosawa
Chem. Commun. 2004, 2732-2733.
Ni(cod)2/PtBu3 system catalyzed the dimerization of terminal alkynes to give (E)-head-to-head dimerization products, in which the stannylacetylene dimer could be applied to a one-pot synthesis of a conjugated enyne, when combined with Migita-Stille coupling.

Stepwise growth of polypalladium chains in 1,4-diphenyl-1,3-butadiene sandwich complexes

Y. Tatsumi, T. Nagai, H. Nakashima, T. Murahashi, and H. Kurosawa
Chem. Commun. 2004, 1430-1431.
A series of multinuclear palladium sandwich complexes supported by two 1,4-diphenyl-1,3-butadiene molecules were prepared by stepwise growth of palladium chains within a sandwich framework. Reaction of palladium(I) dimer, [Pd2(CH3CN)6][BF4]2 with PhCH=CHCH=CHPh afforded dipalladium complexes [Pd2(μ-(1,2,3-η):(4,1',2'-η)-PhCH=CHCH=CHPh)(CH3CN)4][BF4]2.

Reaction of η2-enone and enal-platinum(0) complexes with Lewis acidic compounds

M. Morita, K. Inoue, T. Yoshida, S. Ogoshi, and H. Kurosawa
J. Organomet. Chem. 2004, 689, 894-898
Reaction of η2-enone and enal-Pt(0) complexes Pt(CH2=CHCOR)(PPh3)2 (R = H, Me) with Lewis acidic compounds BX3 (X = F, C6F5) afforded adducts formed by coordination of B to O of the carbonyl group.

Convenient synthesis of Pt(0) olefin complexes by colorimetric reduction of Pt(II) complexes with SmI2

S. Ogoshi, M. Morita, K. Inoue, and H. Kurosawa
J. Organomet. Chem. 2004, 689, 662-665
Homoleptic olefin platinum(0) complexes, Pt(C7H10)3 and Pt(cod)2, were synthesized by the colorimetric reduction of platinum(II) complexes with SmI2 in the presence of 2-norbornene or 1,5-cyclooctadiene.

Synthesis, Structure, and Reactivity of an η3-1-Hydroxyallyl Complex: Protonation of an α,β-Unsaturated Carbonyl Compound Bound to Palladium(0)and Platinum(0)

S. Ogoshi, M. Morita, and H. Kurosawa
J. Am. Chem. Soc. 2003, 125, 9020-9021
The direct addition of a proton to a carbonyl O in an η2-enone Pd complex led to the quantitative formation of η3-1-hydroxyallyl complexes [η3-(CH2CHCR(OH))Pd(PPh3)2][CF3SO3] (R = H and Me).

Perylene-Tetrapalladium Sandwich Complexes

T. Murahashi, T. Uemura, and H. Kurosawa
J. Am. Chem. Soc. 2003, 125, 8436-8437
Bis-perylene-tetrapalladium sandwich complexes, which are the 1st examples of bis-arene sandwich complexes having metal-metal bond chains, were synthesized and structurally characterized.

Reaction of Palladium and Platinum Complexes Bearing α,β-Unsaturated Carbonyl Compounds with Carbon Electrophiles: Control over Site of Electrophilic Attack, Oxygen or Metal

M. Morita, K. Inoue, S. Ogoshi, and H. Kurosawa
Organometallics 2003, 22, 5468-5472.
The reaction of (η2-CH2=CHCHO)M(dppf) (M = Pd, Pt) with methyl triflate yielded η3-methoxyallyl complexes [(η3-CH3OCHCHCH2)M(dppf)2][OTf], and the η3-allyl moiety in these complexes is found to be distorted by X-ray diffraction study.

New direction in organopalladium chemistry: Structure and reactivity of unsaturated hydrocarbon ligands bound to multipalladium units

T. Murahashi, S. Ogoshi, and H. Kurosawa
Chemical Record 2003, 3, 101-111.

New chemistry of η3-allenyl/propargyl complexes of palladium and platinum

S. Ogoshi and H. Kurosawa
Yuki Gosei Kagaku Kyokaishi 2003, 61, 16-25.

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