POSITIVELY CHARGED LIGANDS. THE SYNTHESIS, STRUCTURE, AND BONDING OF SULFONIUM ION COMPLEXES OF TRANSITION METALS AND EVIDENCE FOR A METAL-INDUCED ACCELERATION OF THEIR DEALKYLATION.

Article abstract of DOI:10.1021/ja00351a033

The complexes M(CO)//4 left bracket P(C//6H//5)//2 (CH//2)//2SCH//3 right bracket (M equals Mo, Ia; M equals W, l//react with left bracket O(CH//3)//3 right bracket **4912 BF//4**** minus by methylation of (F**sulfur atom of the chelating (C//6H//5)//2P(CH//2)//2SCH//3 ligand to yield the complexes M(CO)//4 left bracket P(C//6H//1 2(CH//2S(CH//3)//2 right bracket plus plus BF//4**-(M equals Mo, IIa; M equals W, IIb) in which the (C//6H//5)//2P(CH//2)//2S(CH//3)//2** plus ligand is coordinated to the metal atom through both the phosphorus and the positively charged sulfur atom. Compounds Ia and IIa were investigated by X-ray crystallographic methods. For Ia: space group P2//12//12//12//1, a equals 8. 150 (6) A, b equals 14. 229 (6) A, c equals 17. 209(9) A, V equals 1996 (3) A**3, Z equals 4, // RHO //c//a//l//c//d equals 1. 56 g/cm**3. For 1699 reflections (F**2 greater than equivalent to 2. 0 sigma (F)**2), R//F equals 0. 025 and R//w//F equals 0. 022. For IIa: space group P2//1/c, a equals 16. 928 (5) A, b equals 21. 786 (12) A, c equals 13. 900 (9) A, beta equals 106. 38 (4) degree ,V equals 4918 (8) A**3, Z equals 8, p//c//a//1//c//d equals 1. 54 g/cm//3. For 4912 reflections(F**2 greater than equivalent to 3. 0 sigma (F//2)), R//F equals 0. 043 and R//w//F equals 0. 054. The metal atoms in both Ia and IIa have octahedral coordination geometries. The MO-S** plus distance in IIa at 2. 425 (4) A is 0. 135 A shorter than the Mo-S distance in Ia of 2. 560 (1) A.