SYNTHESIS AND REACTIVITY OF RUCP-ASTERISK(KAPPA(2)(P,N)-PH2PCH2CH2NME2)CL - CHELATE-ASSISTED METHYL C-H ACTIVATION AND FORMATION OF THE NOVEL COMPLEX STERISK(KAPPA(3)(P,N,C)-PH2PCH2CH2N(CH2)ME)CL]BPH4

Citation
K. Mauthner et al., SYNTHESIS AND REACTIVITY OF RUCP-ASTERISK(KAPPA(2)(P,N)-PH2PCH2CH2NME2)CL - CHELATE-ASSISTED METHYL C-H ACTIVATION AND FORMATION OF THE NOVEL COMPLEX STERISK(KAPPA(3)(P,N,C)-PH2PCH2CH2N(CH2)ME)CL]BPH4, Organometallics, 16(9), 1997, pp. 1956-1961
Citations number
31
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry Inorganic & Nuclear","Chemistry Inorganic & Nuclear
Journal title
ISSN journal
0276-7333
Volume
16
Issue
9
Year of publication
1997
Pages
1956 - 1961
Database
ISI
SICI code
0276-7333(1997)16:9<1956:SAROR>2.0.ZU;2-X
Abstract
RuCp(kappa(2)(P,N)-Ph2PCH2CH2NMe2)Cl (1) is afforded in 87% yield by the reaction of RuCp(eta(4)-isoprene)Cl with 1 equiv of Ph2PCH2CH2NMe 2 in CH2Cl2 as the solvent. The hemilabile nature of the Ph2PCH2CH2NMe 2 ligand in 1 is revealed by the reaction with carbon monoxide, whereu pon the neutral complex RuCp(kappa(1)(P)-Ph2PCH2CH2NMe2)(Cl)(CO) (2) is obtained bearing the Ph2PCH2CH2NMe2 ligand in kappa(1)(P)-coordinat ed fashion, Chloride abstraction from 1 with TlCF3SO3 led to uCp(kapp a(2)(P,N)-Ph2PCH2CH2NMe2)(eta(1)-OSO2CF3) (3), where CF2SO3- is direct ly bound to the metal center. Both 1 and 3 are convenient precursors f or the synthesis of the cationic vinylidene complex [RuCp(kappa(2)(P, N)-Ph2PCH2CH2NMe2)(=C=CHPh)](+) (4). When chloride abstraction from 1 was performed with NaBPh4 in CH2Cl2 instead of TlCF3SO3 in tetrahydrof uran as the solvent, the novel cationic Ru(IV) complex [RuCp (kappa(3 )(P,N,C)-Ph2PCH2CH2N(CH2)Me)CI](+) (5) was formed. This reaction likel y proceeds via the cationic 16e(-) complex [RuCp(kappa(2)(P,N)-Ph2PCH 2CH2NMe2)](+), which then readily undergoes methyl beta-hydrogen elimi nation to give the cyclometalated cationic hydride complex [RuCp(kapp a(3)(P,N,C)-Ph2PCH2CH2N(CH2)Me)H](+). This latter complex is trapped i n CH2Cl2 or CD2Cl2 as the chloro complex 5. Preliminary results on the catalytic activity of 1 are also presented. Thus, 1 is shown to catal yze the dimerization and cyclotrimerization of some terminal alkynes H C=CR. Whereas with R = Ph, SiMe3, and n-Bu, isomeric mixtures of head- to-head and head-to-tail coupling products are obtained, in the case o f R = COOEt, cyclotrimerization takes place exclusively. X-ray structu res of complexes 1, 3, 4, and 5 are presented.