Inorganic Chemistry p. 2498 - 2504 (1981)
Update date:2022-09-26
Topics:
Lee, Chung-L.I.
Hunt, Catherine T.
Balch, Alan L.
Acetylenes with electron-withdrawing substituents react with Pd2(dpm)2X2 (dpm = (C6H5)2PCH2P(C6H 5)2; X = Cl, Br, I) to form Pd2(dpm)2(μ-acetylene)X2 (acetylene = C2(CF3)2, C2(CO2CH3)2, C2(CO2C2H5)2, HC2CO2H, HC2CO2CH3) which have been characterized by infrared and 31P{1H} and 1H NMR spectroscopy. These acetylene adducts are resistant to acetylene exchange and to protonation. Reaction with methyl isocyanide yields [Pd2(dpm)2(μ-C2{CO2CH 3}2)-(CNCH3)2][[PF6] 2 which is also formed by reaction of [Pd2(dpm)2(μ-CNCH3)(CNCH3) 2][PF6]2 with dimethyl acetylenedicarboxylate. Pd2(dpm)2Cl2 is a catalyst for the cyclotrimerization of dimethyl acetylenedicarboxylate and Pd2-(dpm)2(μ-C2{CO2CH 3}2)Cl2 is formed during the reaction. The reaction of Pd2(dpm)2I2 with maleic anhydride results in the formation of Pd(dpm)I2 and two other incompletely characterized products which can also be obtained through the addition of maleic anhydride to Pd2(dpm)3. Ethylene, norbornadiene, and chlorotrifluoroethene are unreactive toward Pd2(dpm)2Cl2. Phenyl and methyl isothiocyanate react with Pd2(dpm)2Cl2 to yield Pd2(dpm)2(μ-CNR)Cl2 in 50% isolated yield; some Pd2(dpm)2(μ-S)Cl2 is formed in the process.
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(1980)
