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Titolo:
Multi-insertion reactions of isocyanides with zirconium amido silyl complexes
Autore:
Wu, ZZ; Diminnie, JB; Xue, ZL;
Indirizzi:
Univ Tennessee, Dept Chem, Knoxville, TN 37996 USA Univ Tennessee Knoxville TN USA 37996 Dept Chem, Knoxville, TN 37996 USA
Titolo Testata:
ORGANOMETALLICS
fascicolo: 6, volume: 18, anno: 1999,
pagine: 1002 - 1010
SICI:
0276-7333(19990315)18:6<1002:MROIWZ>2.0.ZU;2-P
Fonte:
ISI
Lingua:
ENG
Soggetto:
ANIONIC PI-LIGANDS; PREFERENTIAL SILANE ELIMINATION; TRANSITION-METAL COMPLEXES; BOND METATHESIS MECHANISM; RAY CRYSTAL-STRUCTURES; TERT-BUTYL ISOCYANIDE; CARBON-MONOXIDE; TRIS(TRIMETHYLSILYL)SILYL DERIVATIVES; SPECTROSCOPIC PROPERTIES; MIGRATORY INSERTION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
87
Recensione:
Indirizzi per estratti:
Indirizzo: Xue, ZL Univ Tennessee, Dept Chem, Knoxville, TN 37996 USA Univ TennesseeKnoxville TN USA 37996 em, Knoxville, TN 37996 USA
Citazione:
Z.Z. Wu et al., "Multi-insertion reactions of isocyanides with zirconium amido silyl complexes", ORGANOMETAL, 18(6), 1999, pp. 1002-1010

Abstract

The reactions of (Me2N)(3)ZrSi(SiMe3)(3) (1), (Me2N)(3)ZrSiPh2But(THF)(0.5) (2), and (Me2N)(2)[(Me3Si)(2)N]ZrSi(SiMe3)(3) (3) with 2,6-dimethylphenylisocyanide (ArNC) or tert-butyl isocyanide ((BuNC)-N-t) have been investigated. The first ArNC was found to insert exclusively into the Zr-Si bond incomplex 3 and, in contrast, into the Zr-N bonds in complex 1. Up to 4 equiv of ArNC react with 1 and 2 to give (Me2N)(2)Zr[Si(SiMe3)(3)][eta(2)-C(NMe2)=NAr] (4), (Me2N)Zr[Si(SiMe3)(3)][eta(2)-C(NMe2)=NAr](2) (5), (Me2N)Zr[eta(2)-C(NMe2)=NAr](2){eta(2)-C[Si(SiMe3)(3)]=NAr} (6), Zr[eta(2)-C(NMe2)=NAr](3) {eta(2)-C[Si(SiMe3)(3)]=NAr} (7), and Zr[eta(2)-C(NMe2)=NAr](3)[eta(2)-C(SiPh2But) =NAr] (8). However, 3 reacts with only 2 equiv of ArNC to yield (Me2N)(2)[(Me3Si)(2)N]Zr{eta(2)-C[Si(SiMe3)(3)]=NAr} (9) and (Me2N) [(Me3Si)(2)N]Zr[eta(2)-C(NMe2)=NAr]{eta(2)-C[Si(SiMe3)(3)]=NAr} (10). Complex 2 was found to react with 2 equiv of ButNC to yield a ketenimine complex (Me2N)(3)Zr[N(Bu-t)C(SiPh2But)=C=NBut] (12). The reactions of Zr(NMe2)(4) with ArNC and (BuNC)-N-t were also studied and gave tetrainsertion products Zr[eta(2)-C(NMe2)=NR](4) [R = Bu-t (13), 2,6-dimethylphenyl (14)]. The structures of 7, 12, 13, and 14 have been determined by X-ray crystallography.

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Documento generato il 02/12/20 alle ore 15:04:31