Reactions of acetylenes with noble-metal halides. IX. Decomposition of the complex [Cl(Me2C2)3PdCl]2, particularly to vinylpentamethylcyclopentadiene

The electronic band calculations of noble metal halides are studied to make the high ionic conducting origin of silver and cupper ions clear using the tight-binding method. The d bands of Ag ions are much more weakly coupled with the p bands of halogen ions, while those of Cu ions are much more strongly coupled with the p bands. The strength of p-d hybridization is discussed to connect with the activation energy for the ionic conduction. It is shown that the high ionic conductivity of AgX primary stems from combination of the deformability of the d shell and the weakness of the p-d hybridization.

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Reactions of acetylenes with noble-metal halides.

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(00)94170-6 ◽

1965 ◽

Vol 4 (3) ◽

pp. 254-255 ◽

Cited By ~ 8

Author(s):

P.M. Maitlis ◽

S. McVey

Keyword(s):

Noble Metal ◽

Metal Halides

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Dielectric screening properties in molten noble-metal halides

Journal of Alloys and Compounds ◽

10.1016/j.jallcom.2006.12.161 ◽

2008 ◽

Vol 452 (1) ◽

pp. 182-187 ◽

Cited By ~ 1

Author(s):

Shigeki Matsunaga ◽

Masatoshi Saito ◽

Takahiro Koishi ◽

Shigeru Tamaki

Keyword(s):

Noble Metal ◽

Metal Halides ◽

Dielectric Screening

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Reactions of acetylenes with noble-metal halides. VI. The reactions of 2-butyne with chlorodicarbonylrhodium dimer

Canadian Journal of Chemistry ◽

10.1139/v68-529 ◽

1968 ◽

Vol 46 (20) ◽

pp. 3189-3196 ◽

Cited By ~ 19

Author(s):

J. W. Kang ◽

S. McVey ◽

P. M. Maitlis

Keyword(s):

Noble Metal ◽

Methylene Chloride ◽

Variable Composition ◽

Metal Halides ◽

Dimethylmaleic Anhydride

Chlorodicarbonylrhodium dimer ([Rh(CO)2Cl]2) reacted with 2-butyne at 80° in benzene to give a mixture of compounds which contained hexamethylbenzene, duroquinone, chloro(π-duroquinone)-rhodium dimer, and chloro(π-tetramethylcyclopentadienone)rhodium. At 25° 2-butyne and [Rh(CO)2Cl]2 reacted to give a brown solid of variable composition (C), which could not be purified. Reaction of (C) with CO in methylene chloride gave a related solid (D) also of variable composition. Treatment of (C), or better (D), with an excess of triphenylphosphine gave chloro(dimethylmaleyl)bis(triphenylphosphine)-rhodium and (Ph3P)2RhCOCl. The former was identified by analysis, spectra, and its oxidation to dimethylmaleic anhydride. Reaction of (D) with p-toluidine gave chloro(dimethylmaleyl)carbonylbis(p-toluidine)rhodium, which on treatment with excess triphenylphosphine also gave chloro(dimethyl-maleyl)bis(triphenylphosphine)rhodium.

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