Untersuchungen zur reaktivität von metall-π-komplexen: XXX. (PdPd)-Zweikernkomplexe mit zwei allylgruppen sowie mit einer allylgruppe und einem halogen als brückenliganden

doi:10.1016/S0022-328X(00)91860-6

Journal of Organometallic Chemistry

Volume 179, Issue 4, 30 October 1979, Pages 439-445

https://doi.org/10.1016/S0022-328X(00)91860-6 Get rights and content

Abstract

The reactions of Pd(2-MeC₃H₄)₂ with PdL₂(L = P(i-Pr)₃, PCy₃) in the molar ratio of $11$ produce the binuclear complexes (2-MeC₃H₄)₂Pd₂L₂ in which the bridging 2-methylallyl ligands are symmetrically linked to both metal atoms. The methods of “1 + 1” addition has also been applied to prepare (2-MeC₃H₄(X)Pd₂L₂ (X = Cl, L = P(i-Pr)₃, P(t-Bu)₃, PCy₃; X = I, L = P(i-Pr)₃) which contain one 2-methylallyl and one halogen ligand in a bridging position. Attemps to synthesize similar binuclear complexes with NiNi, PtPt and NiPd bonds failed. The reaction of [C₈H₁₂RhCl]₂ and Pd[P(i-Pr)₃]₂ gives C₈H₁₂Rh[P(i-Pr)₃]Cl.

Zusammenfassung

Die Reaktionen von Pd(2-MeC₃H₄)₂ mit PdL₂ (L = P(i-Pr)₃, PCy₃) im Molverhältnis von $11$ ergeben die Zweikernkomplexe (2-MeC₃H₄)₂Pd₂L₂, in denen die verbrückenden 2-Methylallyl-Liganden symmetrisch an die beiden Metallatome gebunden sind. Die Methode der “1 + 1”-Addition ist ebenfalls anwendbar zur Darstellung der Verbindungen (2-MeC₃H₄)(X)Pd₂L₂ (X = Cl, L = P(i-Pr)₃, P(t-Bu)₃; X = I, L = P(i-Pr)₃), die einen 2-Methylallyl- und einen Halogen-Liganden in einer Brückenposition enthalten. Versuche zur Synthese ähnlicher Zweikernkomplexe mit NiNi-, PtPt- und NiPd-Bindungen schulgen fehl. Die Reaktion von [C₈H₁₂RhCl]₂ und Pd[P(i-Pr)₃]₂ ergibt C₈H₁₂Rh[P(i-Pr)₃]Cl.

Literatur (20)

A. Kühn et al.
J. Organometal. Chem.
(1979)
H. Felkin et al.
J. Organometal. Chem.
(1977)
F. Dawans et al.
J. Organometal. Chem.
(1970)
W. Kuran et al.
Inorg. Chim. Acta
(1975)
M. Aresta et al.
Inorg. Chim. Acta
(1975)
H. Werner et al.
Angew. Chem.
(1977)
H. Werner et al.
Angew. Chem. Int. Ed. Engl.
(1977)
H. Werner et al.
Chem. Ber.
(1977)
Y. Kobayashi et al.
Acta Crystallogr.
(1972)
H. Werner et al.
Z. Naturforsch. B
(1978)

There are more references available in the full text version of this article.

Cited by (31)

Preparation of 2,3-disubstituted indoles by sequential Larock heteroannulation and silicon-based cross-coupling reactions
2009, Tetrahedron
A simple and convergent synthesis of 2,3-disubstituted indoles has been developed using a sequential Larock indole synthesis and silicon-based, cross-coupling reaction. Substituted 2-iodoanilines reacted with an alkynyldimethylsilyl tert-butyl ether to afford indole-2-silanols under the Larock heteroannulation conditions after hydrolysis. The corresponding sodium 2-indolylsilanolate salts successfully engaged in cross-coupling with aryl bromides and chlorides to afford multi-substituted indoles. The development of an alkynyldimethylsilyl tert-butyl ether as a masked silanol equivalent enabled a smooth heteroannulation process and the identification of a suitable catalyst/ligand combination provided for a facile cross-coupling reaction.
Organopalladium complexes containing palladium-palladium bonds
2002, Coordination Chemistry Reviews
Citation Excerpt :
The complex 92 (PdPd 2.679 Å) is generated by the reaction of CpPd(allyl) and phosphine, which is frequently used to generate the catalytically active Pd(0) species [11,136–138]. The sandwich dipalladium(I) complexes [(μ-Cp)2Pd2(PEt3)2] (93) (PdPd 2.673(1) Å) and [(μ-allyl)2Pd2(PPh3)2] (94) (PdPd 2.720 Å) can also be prepared in the same fashion [139–146]. A unique reaction occurred when the 2-chloroallylpalladium complex was used.
Cobalt, rhodium, and iridium annual survey covering the year 1979
1982, Journal of Organometallic Chemistry
Nickel, palladium and platinum, annual survey covering the year 1979
1981, Journal of Organometallic Chemistry
Palladium and Platinum
1981, Coordination Chemistry Reviews
Novel Types of Metal-Metal Bonded Complexes Containing Allyl and Cyclopentadienyl Bridging Ligands
1981, Advances in Organometallic Chemistry
This chapter discusses the novel types of metal–metal bonded complexes, the original synthetic pathway, the real sandwiches, and the structure, bonding, and reaction mechanism of these complexes. Binuclear sandwich-type complexes possessing a metal–metal bonded M₂ unit coordinated by two planar C_nH_n ring systems are very rare. Among dicyclopentadienylmetal species, cobaltocene and nickelocene have been known to react under rather mild conditions. In most cases, the reaction is quite rapid at room temperature, leading to complete formation of the products in a very few minutes. Higher temperatures are only necessary with bulky ligands, such as P-i-Pr₃ or PCy₃ (Cy = cyclo-C₆H₁₁). The more elegant route––which is called for simplicity “the method of [1 + 1]-addition”––may also be used to prepare other binuclear complexes containing either two allyl groups or one allyl group and one halogen in the bridging positions. The two anionic species MeCOO⁻ and 2-MeC₃H₄⁻ are isostructural and isoelectronic, each contributing four electrons when coordinated as bridging ligands. A very fast rotation of the five-membered ring about the axis passing through its center and oriented perpendicular to the Pd–Pd bond takes place. The reactions of the binuclear complexes (X)(Y)M₂L₂ with both electrophilic and nucleophilic reagents can be divided into two categories: those in which the binuclear skeleton is retained and those in which two mononuclear products are formed. The presence of simple π-allyl and π-cyclopentadienyl ligands symmetrically coordinated to an M₂ unit seems to be unique.

View all citing articles on Scopus

View full text

Untersuchungen zur reaktivität von metall-π-komplexen: XXX. (PdPd)-Zweikernkomplexe mit zwei allylgruppen sowie mit einer allylgruppe und einem halogen als brückenliganden

Abstract

Zusammenfassung

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.

Inorg. Chim. Acta

Inorg. Chim. Acta

Angew. Chem.

Angew. Chem. Int. Ed. Engl.

Chem. Ber.

Acta Crystallogr.

Z. Naturforsch. B