ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Insertion of Alkynes into Organonickel Functions as a Synthesis of Vinylnickel CompoundsThe diamagnetic vinylnickel compounds trans-Ni(CR1=CR2R3)Cl(PMe3)2 (1a: R1 = R2 = C6H5, R3 = CH3; 2a: R1 = C6H5, R2 = R3 = CH3; 3a: R1 = R2 = CH3, R3 = C6H5; 4a: R1 = R2 = R3 = C6H5) und Ni(CR1=CR2R3)(acac)(PMe3) (5: R1 = R2 = C6H5, R3 = CH3) are formed by insertion of diphenyl-ethyne and 1-phenylpropyne into methyl- or phenylnickel moieties as Z isomers, that are thermally equilibrated with their E isomers. 1-Phenylethyne and 1-phenylpropyne selectively produce (1-phenylvinyl)nickel compounds. Exchange of halide gives bromides 1b, 2b, 4b and iodides 1c, 2c, 4c, and a cyanide 1d. Action of LiR (R = Me, C≡CCMe3) on 1a followed by reductive elimination yields olefins RR1C=CR2R3 while mineral acids or iodine cleave the Ni—C bonds of 1a to give the corresponding olefins (R = H, I). A high-yield synthesis of chloro(phenyl)bis(trimethylphosphane)nickel is also described.
Notes:
Die diamagnetischen Vinylnickel-Verbindungen trans-Ni-(CR1=CR2R3)Cl(PMe3)2 (1a: R1 = R2 = C6H5, R3 = CH3; 2a: R1 = C6H5, R2 = R3 = CH3; 3a: R1 = R2 = CH3, R3 = C6H5; 4a: R1 = R2 = R3 = C6H5) und Ni(CR1=CR2R3)(acac)(PMe3) (5: R1 = R2 = C6H5, R3 = CH3) bilden sich durch Einschiebung von Diphenylethin und 1-Phenylpropin in Methyl- oder Phenyl-nickel-Einheiten als Z-Isomere, die thermisch mit ihren E-Isomeren ins Gleichgewicht gebracht werden. 1-Phenylethin und 1-Phenylpropin ergeben selektiv (1-Phenylvinyl)nickel-Verbindungen. Austausch von Halogen liefert die Bromide 1b, 2b, 4b, die Iodide 1c, 2c, 4c und ein Cyanid 1d. Einwirken von LiR (R = Me, C≡CCMe3) auf 1a mit anschließender reduktiver Eliminierung ergibt Olefin RR1C=CR2R3, während Mineralsäuren oder Iod die Ni—C-Bindungen von 1a spalten und die entsprechenden Olefine (R = H, I) erzeugen. Eine ergiebige Synthese von Chloro(phenyl)bis(trimethylphosphan)nickel wird ebenfalls beschrieben.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19881210615
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