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Titolo:
The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: nitrogen alkylation of an eta(2)-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts
Autore:
Shin, JH; Savage, W; Murphy, VJ; Bonanno, JB; Churchill, DG; Parkin, G;
Indirizzi:
Columbia Univ, Dept Chem, New York, NY 10027 USA Columbia Univ New York NY USA 10027 iv, Dept Chem, New York, NY 10027 USA
Titolo Testata:
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
fascicolo: 11, , anno: 2001,
pagine: 1732 - 1753
SICI:
1472-7773(2001):11<1732:TSSARO>2.0.ZU;2-I
Fonte:
ISI
Lingua:
ENG
Soggetto:
CATIONIC ALKYLBIS(CYCLOPENTADIENYL)TITANIUM COMPLEXES; CRYSTAL-STRUCTURE; MOLECULAR-STRUCTURE; ELECTRONIC-STRUCTURE; INSERTION REACTIONS; NITRILE COMPLEXES; TRANSITION-METALS; OXO COMPLEXES; MOLYBDENOCENE; TUNGSTENOCENE;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
109
Recensione:
Indirizzi per estratti:
Indirizzo: Parkin, G Columbia Univ, Dept Chem, New York, NY 10027 USA Columbia Univ New York NY USA 10027 hem, New York, NY 10027 USA
Citazione:
J.H. Shin et al., "The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: nitrogen alkylation of an eta(2)-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts", J CHEM S DA, (11), 2001, pp. 1732-1753

Abstract

An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(Cp-But)(2)Mo} (Cp-But = C5H4But), has demonstrated that the eta (2)-acetonitrile ligand in (Cp-But)(2)Mo(eta (2)-MeCN) may be alkylated by RI (R = Me, Et) at nitrogen to give iminoacyl derivatives, [(Cp-But)(2)Mo(eta (2)-MeC=NR)](+), which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (Cp-But)(2)Mo(EPh)H (E = S, Se, Te) have been obtained by reaction of (Cp-But)(2)MoH2 with Ph2E2, and may be alkylated by MeI to give the chalcogenoether adducts [(Cp-But)(2)Mo(PhEMe)H]I. Dynamic NMR studies on [(Cp-But)(2)Mo(PhEMe)H](+) indicate that the barrier to inversion at the chalcogen increases in the sequence S < Se < Te. The oxo complex (Cp-But)(2)MoO reacts with 2 equivalents of Me3SiX (X = Cl, Br, I, O2CMe, O3SMe) to yield (Cp-But)(2)MoX2; for X = CN and NCS, (Cp-But)(2)Mo(OSiMe3)X, the product of reaction with 1 equivalent may be isolated. (Cp-But)(2)Mo(OSiMe3)X (X = CN, NCS) reacts with Me3SiNCS to give the thiocyanate complex (Cp-But)(2)Mo(SCN)X, rather than the isocyanate isomer, (Cp-But)(2)Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include: (Cp-But)(2)MoX2 (X = H, Cl, Br, I, Me, CH2Ph, CH2SiMe3), (Cp-But)(2)MoL (L = CO, C2H4, C2H2, MeCN, PMe3), [(Cp-But)(2)Mo(mu -E)](2), (Cp-But)(2)Mo(eta (2)-E-2) and (Cp-But)(2)Mo(EPh)(2) (E = S, Se, Te).

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 26/09/20 alle ore 11:44:53