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Titolo:
Monocarbollide complexes of molybdenum and tungsten: functionalization through reactions at a cage boron centre
Autore:
Du, SW; Franken, A; Jelliss, PA; Kautz, JA; Gordon, F; Stone, A; Yu, PY;
Indirizzi:
Baylor Univ, Dept Chem & Biochem, Waco, TX 76798 USA Baylor Univ Waco TX USA 76798 iv, Dept Chem & Biochem, Waco, TX 76798 USA
Titolo Testata:
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
fascicolo: 12, , anno: 2001,
pagine: 1846 - 1856
SICI:
1472-7773(2001):12<1846:MCOMAT>2.0.ZU;2-W
Fonte:
ISI
Lingua:
ENG
Soggetto:
CARBORANE COMPLEXES; CHEMISTRY; MOLECULES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
26
Recensione:
Indirizzi per estratti:
Indirizzo: Stone, A Baylor Univ, Dept Chem & Biochem, Waco, TX 76798 USA Baylor UnivWaco TX USA 76798 Chem & Biochem, Waco, TX 76798 USA
Citazione:
S.W. Du et al., "Monocarbollide complexes of molybdenum and tungsten: functionalization through reactions at a cage boron centre", J CHEM S DA, (12), 2001, pp. 1846-1856

Abstract

Reactions of the salts [N(PPh3)(2)][2,2,2-(CO)(3)-2-PPh3-closo-2,1-MCB10H11] (M = Mo or W) with CF3SO3Me or H2SO4 in the presence of donor molecules L afford zwitterionic molecules [2,2,2-(CO)(3)-2-PPh3-7-L-closo-2,1-MCB10H10] [L = OEt2, O(CH2)(4), cyclo-1,4-O(CH2)(4)O, SMe2, S(CH2)(4), cyclo-1,4,7-S-3(CH2)(6), NCBut or CNC6H3Me2-2,6]. The exopolyhedral group L is attached to a beta -boron atom in the CBBBB ring coordinated to the metal, a feature confirmed by an X-ray crystallographic study of [2,2,2-(CO)(3)-2-PPh3-7-(CNC6H3Me2-2,6)-closo-2,1-MoCB10H10]. The molecules [2,2,2-(CO)(3)-2-PPh3-7-L-closo-2,1-WCB10H10] [L = OEt2 or O(CH2)(4)] in THF (tetrahydrofuran) react with Me3NO, with addition of [PPh4]Br, to give the salts [PPh4][2,2,2-(CO)(3)-2-PPh3-7-R-closo-2,1-WCB10H10] [R = OEt or O(CH2)(3)CHO]. These products on treatment with CF3SO3Me in CH2Cl2 give the zwitterionic molecules [2,2,2-(CO)(3)-2-PPh3-7-{O(Me)R}-closo-2,1-WCB10H10] (R = Et or Bu-n). Singlecrystal X-ray diffraction studies established the structures of [PPh4][2,2,2-(CO)(3)-2-PPh3-7-OEt-closo-2,1-WCB10H10] and [2,2,2-(CO)(3)-2-PPh3-7-{O(Me)Bu-n}-closo-2,1-WCB10H10]. In NCMe the reagents [N(PPh3)(2)][2,2,2-(CO)(3)-2-PPh3-closo-2,1-MCB10H11] react with CF3SO3Me to yield [2,2,2-(CO)(3)-2-PPh3-7-{N(Me)=C(H)Me}-closo-2,1-MCB10H10] (M = Mo or W), compounds in which an imine substituent is bonded to the cage system, a feature confirmed byan X-ray diffraction study of the tungsten species. Similarly, the compounds [N(PPh3)(2)][2,2,2-(CO)(3)-2-PPh3-closo-2,1-MCB10H11] react with CNBut and CF3SO3Me to give a mixture of isomers of [2,2,2-(CO)(3)-2-PPh3-7-{N(Bu-t)=C(H)Me}-closo-2,1-MCB10H10] (M = Mo or W) with E and Z configurations forthe BN(Bu-t)=C(H)Me group.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 21/01/21 alle ore 04:23:05