Accession Number : AD0696432

Title :   PROBLEMS RELATING TO AMIDO-DERIVATIVES OF METALS AND METALLOIDS.

Descriptive Note : Final technical rept. May 68-Apr 69,

Corporate Author : SUSSEX UNIV BRIGHTON (ENGLAND) CHEMICAL LAB

Personal Author(s) : Cardin,D. J. ; Keppie,S. A. ; Lappert,M. F. ; Poland,J. S. ; Sanger,A. R.

Report Date : AUG 1969

Pagination or Media Count : 200

Abstract : Insertion reactions of some metal (B, Si, Ge, Sn(IV), Ti(IV), Zr(IV), and Hf(IV), amides with nitriles, diketene, crotonaldehyde, lambda-butyrolactone, and propylene sulphide are described along with their reactions with the protic species ethyleneimine, alkynes and pentafluorobenzene. Also discussed is the metathetical exchange reactions with boron trifluoride and with fluorcarbons and some seven co-ordinate manganese(III) complexes. Next a comprehensive summary of earlier work on (a) reactions of organo-sodium and -lithium reagents with unsaturated compounds, (b) insertion reactions of nitriles, and (c) reactions of organolithium reagents with metal carbonyls is presented; plus the results of investigations of (i) insertions of benzonitrile into lithium dimethylamide and bis(trimethylsilyl)amide, (ii) reactions of acetonitrile with the same amides, and (iii) reactions of lithium dimethylamide with some Group(VIA) metal carbonyls. The syntheses of new organometallic diazoalkanes along with their reactions: 1,3-cyclo-additions to some unsaturated substrates; 1,3-insertion reactions into the M-H bond of pi-C5H5(CO)3 M-H (M = Mo or W) so afford azo-compounds; and metal-carbon cleavage reactions. The work also provides an alternative synthesis of several such compounds and also of pi-cyclopentadienylmetal hydrides by way of a novel oxidative addition of sigma-cyclopentadienyl metallates or of cyclopentadiene to metal carbonyl residues. Mentioned are the novel dialkylamides of Ti(III).

Descriptors :   (*COMPLEX COMPOUNDS, *TRANSITION METALS), (*ORGANIC NITROGEN COMPOUNDS, COMPLEX COMPOUNDS), (*METALORGANIC COMPOUNDS, CHEMICAL REACTIONS), SYNTHESIS(CHEMISTRY), NITRILES, AMIDES, CHELATE COMPOUNDS, TITANIUM COMPOUNDS, ZIRCONIUM COMPOUNDS, HAFNIUM COMPOUNDS, LITHIUM COMPOUNDS, VANADIUM COMPOUNDS, ADDITION REACTIONS, AMINES, IMINES, TIN COMPOUNDS, INFRARED SPECTRA, NUCLEAR MAGNETIC RESONANCE, GREAT BRITAIN

Subject Categories : Organic Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE