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Titolo:
Silylimido complexes of niobium and tantalum at the limit of pi-bond saturation
Autore:
Schorm, A; Sundermeyer, J;
Indirizzi:
Univ Marburg, Fachbereich Chem, D-35032 Marburg, Germany Univ Marburg Marburg Germany D-35032 eich Chem, D-35032 Marburg, Germany
Titolo Testata:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
fascicolo: 11, , anno: 2001,
pagine: 2947 - 2955
SICI:
1434-1948(200111):11<2947:SCONAT>2.0.ZU;2-Z
Fonte:
ISI
Lingua:
ENG
Soggetto:
D-METAL ACIDS; HIGHER-VALENT DERIVATIVES; RAY CRYSTAL-STRUCTURE; IMIDO COMPLEXES; HALF-SANDWICH; ETHYLENE POLYMERIZATION; ORGANOIMIDO-COMPLEXES; ISOLOBAL RELATIONSHIP; MOLECULAR-STRUCTURE; TRANSITION-METALS;
Keywords:
niobium; tantalum; N ligands; cyclopentadienyl ligands; rearrangements;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
76
Recensione:
Indirizzi per estratti:
Indirizzo: Sundermeyer, J Univ Marburg, Fachbereich Chem, Hans Meerwein Str, D-35032 Marburg, Germany Univ Marburg Hans Meerwein Str Marburg Germany D-35032 any
Citazione:
A. Schorm e J. Sundermeyer, "Silylimido complexes of niobium and tantalum at the limit of pi-bond saturation", EUR J INORG, (11), 2001, pp. 2947-2955

Abstract

Convenient strategies towards the synthesis of silylimido niobium and -tantalum complexes of the metallocene and half-sandwich type are reported. Bent metallocenes [(eta (5)-C5H5)(2)M(NSiMe3)Cl] (M = Nb: 1a; Ta: 1b) and [(eta (5)-C5H5)(2)M(NSiMe3)(eta (1)-C5H5)] (M = Nb: 2a; Ta: 2b) are synthesizedby reaction of [M(NSiMe3)Cl-3(py)(2)] with 2 or 3 equiv. NaCp, respectively. Half-sandwich type silylimido complexes [(eta (5)-C5Me5)M(NSiMe3)Cl-2] (M = Nb: 3a; Ta: 3b) cannot selectively be obtained from the (pyridine)(silylimido) precursor complexes. However, their synthesis is accomplished by reaction of [(eta (5)-C5Me5)MCl4] with LiN(SiMe3)(2), On the other hand pyridine silylimido complexes are perfect starting materials for the synthesis of the related hydridotris-(pyrazolyl)borato complexes [Tp*M(NSiMe3)Cl-2] [M= Nb: 4a; Ta; 4b; Tp* = kappa (3)-HB(3,5-Me(2)pz)(3)]. A comparative studyof the a,ir-donor capability of isoelectronically related tert-butyl- and trimethylsilylimido ligands in complexes [(eta -C5H5)(2)Ta(NR)(eta (1)-C5H5)] (R = SiMe3: 2b; tBu: 2c) is presented. With respect to solid-state structural investigations and solution variable-temperature NMR-spectroscopic studies on the dynamic exchange process of eta (5)- and eta (1)-bonded cyclopentadienyl rings in 2b,c, tert-butlyimido ligands are better donors than silylimido ligands, and both are better donors towards a d(0) metal center than an eta (5)-C5H5 ligand.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 26/09/20 alle ore 11:23:16