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• W2000657835 endingPage "72" @default.
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• W2000657835 abstract "The synthesis and reaction behavior of the penta-coordinated chlorosilanes [C6H4CH2N(CH3)2-2]Si(Cl)(R)(R′) [3a: R=R′=Cl; 3b: R=R′=CH3; 3c: R=C1, R′=CH3; 3d: R=Cl, R′=CHCH2; 3e: R=CH3, R′=CHCH2] are discussed. Compounds 3a–e can be obtained by the reaction of LiC6H4CH2N(CH3)2-2 (1) with stoichiometric amounts of (R)(R′)SiCl2 (2) in high yields and give access to a versatile reaction chemistry on substitution of the chlorine atoms by many of the diverse nucleophiles used. Hydrolysis of compound 3d produces oligomeric {[C6H4CH2N(CH3)2-2](CH2CH)SiO}n (4a), whereas 3e yields the disiloxane {[C6H4CH2N(CH3)2-2](CH2CH)(CH3)Si}2O (4b). Alcoholysis of compounds 3d and 3e in presence of NEt3 affords [C6H4CH2N(CH3)2-2](CH2CH)(CH3)Si(OCH3) (5a) or [C6H4CH2N(CH3)2-2](CH2CH)Si(OR)2 [5b: R=CH3, 5c: R=C2H5, 5d: R=iC3H7], respectively. Compound 5b can be transferred to the difluorosilane derivative [C6H4CH2N(CH3)2-2](CH2CH)SiF2 (6) by its reaction with BF3*O(C2H5)2, while treatment with LiAlH4 produces the silane [C6H4CH2N(CH3)2-2](CH2CH)SiH2 (7a). Moreover, hypervalent silanes are accessible by the reaction of chloro-functionalized 3d or 3e with LiAlH4 whereby compounds [C6H4CH2N(CH3)2](H2CCH)Si(H)(R) (7a: R=H; 7b: R=CH3) are formed in good yields. Metathesis reaction of compounds 3b–e with LiR reagents [R=CCR′, NHC6H2(CH3)3-2,4,6, P(C6H5)2] produces [C6H4CH2N(CH3)2-2](CH3)(R)(SiCCR′) [reaction of 3b or 3e with LiCCR′; 8a: R=CH3, R′=C6H5; 8b: R=CH3, R′=Si(CH3)3; 8c: R=CHCH2, R′=C6H5; 8d: R=CHCH2, R′=Si(CH3)3], [C6H4CH2N(CH3)2-2](R)Si(CCR′)2 [reaction of 3c or 3d with LiCCR′; 9a: R=CH3, R′=C6H5; 9b: R=CHCH2, R′=C6H5; 9c: R=CHCH2, R=Si(CH3)3], [C6H4CH2N(CH3)2-2](H2CCH)Si[HNC6H2(CH3)3-2,4,6]2 [reaction of 3d with LiNHC6H2(CH3)3-2,4,6; 10] or [C6H4CH2N(CH3)2-2](H2CCH)Si[P(C6H5)2]2 [reaction of 3d with LiP(C6H5)2; 11]. The solid state structures of 3c and 3d are reported. Complex 3c crystallizes in the monoclinic space group P21/c with a=8.918(5), b=11.557(3), c=12.830(7) Å; β=108.17(4)°, V=1256(5) Å3 and Z=4; 3d crystallizes in the monoclinic space group P21 with a=6.625(3), b=8.574(6), c=11.281(8) Å; β=88.16(5)°, V=640.5(7) Å3 and Z=2. The central silicon atom in compounds 3c and 3d shows an essentially distorted trigonal-bipyramidal coordination sphere, with the axial positions occupied by the nitrogen donor atom and one chloro ligand. Dynamic 1H-NMR studies confirm that the same geometry is adopted in solution." @default.
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• W2000657835 date "1998-07-01" @default.
• W2000657835 modified "2023-10-16" @default.
• W2000657835 title "Penta-coordinated chlorosilanes: reaction chemistry, structure and bonding" @default.
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• W2000657835 doi "https://doi.org/10.1016/s0022-328x(98)00554-3" @default.
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