THE FIRST PERALKYLATED PHOSPHINO(STIBINO)METHANES AND THEIR ORGANOMETALLIC RHODIUM COMPLEXES

Citation
M. Manger et al., THE FIRST PERALKYLATED PHOSPHINO(STIBINO)METHANES AND THEIR ORGANOMETALLIC RHODIUM COMPLEXES, Chemistry, 3(9), 1997, pp. 1442-1450
Citations number
60
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry
Journal title
Chemistry → ACNP
ISSN journal
0947-6539
Volume
3
Issue
9
Year of publication
1997
Pages
1442 - 1450
Database
ISI
SICI code
0947-6539(1997)3:9<1442:TFPPAT>2.0.ZU;2-Q
Abstract
The first representatives of phosphino(stibino)methanes R2PCH2Sb- R'(2 ) (3-5) with bulky alkyl or cycloalkyl groups R and R' were prepared i n two steps from Ph3SnCH2I via the isolated stannylated phosphanes Ph3 SnCH2PR2 (1, 2) as intermediates. X-ray structural analysis of 5 (R = C6H11, R' = tBu) reveals that the lone pairs and the substituents R an d R' at phosphorus and antimony and the hydrogen atoms of the CH2 brid ge adopt staggered conformations. Treatment of [{C8H12RhCl}(2)] with 3 -5 affords the neutral compounds [RhCl(eta(4)-C8H12)(k-P-R2PCH2SbR'(2) )](6-8), of which 7 and 8 react with CH3MgI to give the corresponding methylrhodium derivatives [RhCH3(eta(4)-C8H12(k-P-R-2-PCH2SbR'(2))] (9 , 10). Cationic complexes [Rh(eta(4)-C8H12)(k(2)-P,Sb-R2PCH2SbR'(2))]- X (X = PF6: 11a, 12a, 13; X = BPh4: 11b, 12b) containing the phosphin o(stibino)methanes as chelating ligands were obtained either from [{C8 H12RhCl}(2)], R2PCH2SbR'(2) and MX, or (for 13) from 8 and AgPF6. Comp ound 12a (R = iPr, R' = tBu was characterized by X-ray crystallography . The PF6 salts 11a, 12a, and 13 react with CH2N2 by insertion of CH2 into the Rh-Sb bond to yield the complexes 14-16, the First examples o f transition-metal compounds with Sb ylides as ligands. Treatment of B Ph4 salts 11b and 12b with H-2 gives the half-sandwich-type complexes [(eta(6)-C6H5BPh3)Rh(k(2)-P,Sb-R2PCH2SbR'(2))] (17, 18), in which the tetraphenylborate is coordinated like a substituted arene to the metal center.