Convenient Method for the Synthesis of Chloro-Bridged Methyl- and Acetylpalladium(II) Dimers

Folami T. Ladipo; Gordon K. Anderson

doi:10.1021/om00013a044

Convenient Method for the Synthesis of Chloro-Bridged Methyl- and Acetylpalladium(II) Dimers

Folami T. Ladipo, Gordon K. Anderson

Chemistry

Research output: Contribution to journal › Article › peer-review

100 Scopus citations

Abstract

A series of chloro-bridged methylpalladium(II) dimers of the type [ Pd₂(μ -Cl)₂ Me₂L₂] (la-h; L = PEt₃, PMePh₂, PPh₃, P(CH₂Ph)₃, P(OMe)₃, AsPh₃, CNBu^t, 2,6-lutidine) has been prepared from [PdClMe(cod)] and 1 equiv of the appropriate ligand. Cis and trans isomers may be identified where L = PEt₃ or CNBu^t. Addition of a second equivalent of PEt₃ results in a bridge-splitting reaction to give trans-[PdClMe(PEt₃)₂] (2a), but this process may be reversed by addition of further [PdClMe(cod)]. Carbonylation of [PdClMe(cod)] yields the corresponding acetyl complex, and treatment of the latter with PEt₃, AsPh₃, or CNBu^t leads to the acetylpalladium dimers [Pd₂(μ-Cl)₂(COMe)₂L₂] (3a,f,g). Reaction of 3a with PEt₃ produces trans- [PdCl(COMe) (PEt₃)₂] (4a), but this may also be reversed by addition of further [PdCl- (COMe)(cod)]. Addition of excess CNBu^t to [PdClMe(cod)] generates the iminoacyl complex trans- [PdCl{C(═NBu^t)Me}(CNBu^t)₂] (6g).

Original language	English
Pages (from-to)	303-306
Number of pages	4
Journal	Organometallics
Volume	13
Issue number	1
DOIs	https://doi.org/10.1021/om00013a044
State	Published - Jan 1 1994

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Convenient Method for the Synthesis of Chloro-Bridged Methyl- and Acetylpalladium(II) Dimers",

abstract = "A series of chloro-bridged methylpalladium(II) dimers of the type [ Pd2(μ -Cl)2 Me2L2] (la-h; L = PEt3, PMePh2, PPh3, P(CH2Ph)3, P(OMe)3, AsPh3, CNBut, 2,6-lutidine) has been prepared from [PdClMe(cod)] and 1 equiv of the appropriate ligand. Cis and trans isomers may be identified where L = PEt3 or CNBut. Addition of a second equivalent of PEt3 results in a bridge-splitting reaction to give trans-[PdClMe(PEt3)2] (2a), but this process may be reversed by addition of further [PdClMe(cod)]. Carbonylation of [PdClMe(cod)] yields the corresponding acetyl complex, and treatment of the latter with PEt3, AsPh3, or CNBut leads to the acetylpalladium dimers [Pd2(μ-Cl)2(COMe)2L2] (3a,f,g). Reaction of 3a with PEt3 produces trans- [PdCl(COMe) (PEt3)2] (4a), but this may also be reversed by addition of further [PdCl- (COMe)(cod)]. Addition of excess CNBut to [PdClMe(cod)] generates the iminoacyl complex trans- [PdCl{C(═NBut)Me}(CNBut)2] (6g).",

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N2 - A series of chloro-bridged methylpalladium(II) dimers of the type [ Pd2(μ -Cl)2 Me2L2] (la-h; L = PEt3, PMePh2, PPh3, P(CH2Ph)3, P(OMe)3, AsPh3, CNBut, 2,6-lutidine) has been prepared from [PdClMe(cod)] and 1 equiv of the appropriate ligand. Cis and trans isomers may be identified where L = PEt3 or CNBut. Addition of a second equivalent of PEt3 results in a bridge-splitting reaction to give trans-[PdClMe(PEt3)2] (2a), but this process may be reversed by addition of further [PdClMe(cod)]. Carbonylation of [PdClMe(cod)] yields the corresponding acetyl complex, and treatment of the latter with PEt3, AsPh3, or CNBut leads to the acetylpalladium dimers [Pd2(μ-Cl)2(COMe)2L2] (3a,f,g). Reaction of 3a with PEt3 produces trans- [PdCl(COMe) (PEt3)2] (4a), but this may also be reversed by addition of further [PdCl- (COMe)(cod)]. Addition of excess CNBut to [PdClMe(cod)] generates the iminoacyl complex trans- [PdCl{C(═NBut)Me}(CNBut)2] (6g).

AB - A series of chloro-bridged methylpalladium(II) dimers of the type [ Pd2(μ -Cl)2 Me2L2] (la-h; L = PEt3, PMePh2, PPh3, P(CH2Ph)3, P(OMe)3, AsPh3, CNBut, 2,6-lutidine) has been prepared from [PdClMe(cod)] and 1 equiv of the appropriate ligand. Cis and trans isomers may be identified where L = PEt3 or CNBut. Addition of a second equivalent of PEt3 results in a bridge-splitting reaction to give trans-[PdClMe(PEt3)2] (2a), but this process may be reversed by addition of further [PdClMe(cod)]. Carbonylation of [PdClMe(cod)] yields the corresponding acetyl complex, and treatment of the latter with PEt3, AsPh3, or CNBut leads to the acetylpalladium dimers [Pd2(μ-Cl)2(COMe)2L2] (3a,f,g). Reaction of 3a with PEt3 produces trans- [PdCl(COMe) (PEt3)2] (4a), but this may also be reversed by addition of further [PdCl- (COMe)(cod)]. Addition of excess CNBut to [PdClMe(cod)] generates the iminoacyl complex trans- [PdCl{C(═NBut)Me}(CNBut)2] (6g).

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Convenient Method for the Synthesis of Chloro-Bridged Methyl- and Acetylpalladium(II) Dimers

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