Organic‐Inorganic Hybrids based on Polyoxometalates. Part 8 Synthesis and Spectroscopic Characterization of the Heterosilylated Anions [PW 9 O 34 ( t BuSiO) 3 (SiR)] 3‐ (R = ‐CH 3 , ‐CH=CH 2 , ‐CH 2 ‐CH=CH 2 , ‐(CH 2 ) 4 ‐CH=CH 2 ) ‐ X‐ray Crystal Structure of [ n Bu 4 N] 3 [PW 9 O 34 ( t BuSiO) 3 (SiCH 2 ‐CH=CH 2 )]

The reaction of the open‐structure anion [PW 9 O 34 ( t BuSiOH) 3 ] 3‐ with RSiCl 3 (R = (CH 2 ) n CH=CH 2 (n = 0, 1, 4)) affords [PW 9 O 34 ( t BuSiO) 3 (SiR)] 3‐ heterosilylated capped hybrid compounds. These complexes were characterized by infrared spectroscopy and in solution by multinuclear ( 1 H, 29 Si, 31 P and 183 W) NMR. Crystals of [ n Bu 4 N] 3 [PW 9 O 34 ( t BuSiO) 3 Si(CH 2 ‐CH=CH 2 )] are orthorhombic, space group P2 1 2 1 2 1 (N o 19), with lattice constants a = 15.599(2) Å, b = 23.963(5) Å, c = 26.886(1) Å, V = 10.050(3) Å 3 , and Z = 4.