131120-56-4Relevant articles and documents
Penta-coordinated chlorosilanes: Reaction chemistry, structure and bonding
Weinmann, Markus,Gehrig, Anja,Schiemenz, Berthold,Huttner, Gottfried,Nuber, Bernhard,Rheinwald, Gerd,Lang, Heinrich
, p. 61 - 72 (2007/10/03)
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 = Cl, 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 BF*3O(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)](H 2C=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](H 2C=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 with a = 8.918(5), b= 11.557(3), c= 12.830(7) A; β= 108.17(4)°, V = 1256(5) A3 and Z = 4; 3d crystallizes in the monoclinic space group P21 with a = 6.625(3), b = 8.574(6), c = 11.281(8) A; β= 88.16(5)°, V = 640.5(7) A3 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.
