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Phospha‐ and Arsaalkenes RE=C(NMe 2 ) 2 (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents (Eur. J. Inorg. Chem. 26/2007)
Author(s) -
Weber Lothar
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200790065
Subject(s) - phosphinidene , chemistry , ligand (biochemistry) , electrophile , substituent , cycloaddition , stereochemistry , yield (engineering) , nucleophile , ring (chemistry) , reagent , medicinal chemistry , catalysis , organic chemistry , biochemistry , materials science , receptor , metallurgy
The cover picture shows the reaction between the phosphavinylidene complexes [(η 5 ‐C 5 H 5 )(CO) 2 M=P=C(SiMe 3 ) 2 ] and the inversely polarized phosphaalkene t BuP=C(NMe 2 ) 2 , which affords η 3 ‐1,2‐diphosphaallyl complexes by smooth transfer of the phosphinidene unit onto the electrophilic ligand of the precursors. The molecular structure underlines the unsymmetrical η 3 ‐ligation of the heteroallyl ligand to the metal with the tert ‐butyl substituent syn to the central phosphorus atom. Treatment of the phosphavinylidene complexes with P ‐aroylphosphaalkenes leads to decomposition. In contrast, phosphavinylidene complexes and As ‐aroylarsaalkenes yield complexes featuring cyclic phosphenium ligands with an As=C bond. It is believed that the first step of this process is a formal [2+1] cycloaddition between the P=C bond and the aroylarsinidine to give a three‐membered ring, which subsequently incorporates the CO unit to afford the final product. In all cases, tetrakis(dimethylamino)ethene is formed as a byproduct. Details are presented in the Microreview by L. Weber on p. 4095 ff.