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Titolo:
THERMOCHEMICAL ASPECTS OF ARENE C-H ACTIVATION BY TANTALUM SILYL COMPLEXES - RELATIVE TA-SI AND TA-C BOND ENTHALPIES
Autore:
JIANG Q; PESTANA DC; CARROLL PJ; BERRY DH;
Indirizzi:
UNIV PENN,DEPT CHEM PHILADELPHIA PA 19104 UNIV PENN,DEPT CHEM PHILADELPHIA PA 19104 UNIV PENN,RES STRUCT MATTER LAB PHILADELPHIA PA 19104
Titolo Testata:
Organometallics
fascicolo: 9, volume: 13, anno: 1994,
pagine: 3679 - 3691
SICI:
0276-7333(1994)13:9<3679:TAOACA>2.0.ZU;2-M
Fonte:
ISI
Lingua:
ENG
Soggetto:
RAY CRYSTAL-STRUCTURE; TRANSITION-METAL COMPLEXES; NICKEL-CATALYZED REACTIONS; ETA-2-SILANIMINE COMPLEXES; TRIMETHYLSILYL DERIVATIVES; ETA-2-DISILENE COMPLEXES; DISRUPTION ENTHALPIES; DISSOCIATION ENERGIES; DISILENE COMPLEXES; REACTION CHEMISTRY;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Science Citation Index Expanded
Citazioni:
101
Recensione:
Indirizzi per estratti:
Citazione:
Q. Jiang et al., "THERMOCHEMICAL ASPECTS OF ARENE C-H ACTIVATION BY TANTALUM SILYL COMPLEXES - RELATIVE TA-SI AND TA-C BOND ENTHALPIES", Organometallics, 13(9), 1994, pp. 3679-3691

Abstract

Tantalum(III) silyl complexes, Cp(2)Ta(L)(SiR(3)) (L = PMe(3), CO), are reactive toward the C-H bonds of unhindered arenes such as benzene,toluene, and m-xylene. The sterically hindered silyl complex Cp(2)Ta(PMe(3))(Si(t-Bu)(2)H) (1) reacts in neat arenes to produce the corresponding aryl complexes, Cp(2)Ta(PMe(3))(Ar), in high yields. However, complexes with smaller silyl ligands give equilibrium mixtures of silyland aryl complexes in which the silyl is favored. Thermodynamic studies of this system have permitted the first direct comparison of Si-H and C-H bond activation by the same metal center and allow the estimation of relative Ta-C and Ta-Si bond dissociation enthalpies(BDE's). It is found that the Ta-Si bonds in 1 and in Cp(2)Ta(PMe(3))(SiMe(3)) (6)are respectively 5.4 and 7.9 kcal mol(-1) weaker than the Ta-phenyl bond in Cp(2)Ta(PMe(3))(Ph) (3). However, metal-phenyl bonds are generally much stronger than metal-alkyl bonds and the Ta-Si BDE's are probably comparable to or greater than the strength of a tantalum-alkyl bond. As expected, the bulkier silyl exhibits the weaker Ta-Si BDE, but surprisingly the lower stability of 1 with respect to the phenyl complex 3 is primarily due to a large and favorable entropy change (34 +/- 3eu) resulting from the release of steric congestion upon converting the silyl into the phenyl complex. The high reactivity of tantalum silyls toward arene C-H bond activation can also be combined with the facile reaction of tantalum alkyls with silanes to yield the silane-catalyzed conversion of Cp(2)Ta(L)(R) (R = alkyl; L = PMe(3), CH2=CH2) complexes into the corresponding aryl complexes. Complexes Cp(2)Ta(PMe(3))(Si(t-Bu)(2)H) (1), Cp(2)Ta(CO)(Si-(t-Bu)(2)H) (8), and Cp(2)Ta(CO)(SiMe(3)) (9) have been structurally characterized by single crystal X-raydiffraction studies.

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Documento generato il 27/11/20 alle ore 02:10:36