99248-63-2Relevant academic research and scientific papers
Synthesis and reactivity of two monomeric tungsten(IV) phenoxide complexes
Listemann, Mark L.,Schrock, Richard R.,Dewan, John C.,Kolodziej, Richard M.
, p. 264 - 271 (2008/10/08)
W(DIPP)4 (DIPP = O-2,6-C6H3-i-Pr2) has been prepared by adding LiDIPP to WCl4(Et2S)2. W(DMP)4 (DMP = O-2,6-C6H3Me2) can be prepared by an analogous procedure or by reducing trans-W(DMP)4Cl2 with sodium in ether. W(DIPP)4 belongs to the space group C2/c with a = 30.557 (5) ?, b = 13.434 (2) ?, c = 23.312 (3) ?, β = 91.99 (1)°, V = 9153.6 ?3, and Z = 8. Final R1 = 0.042 and R2 = 0.046. W(DIPP)4 contains a ruffled distorted square planar WO4 core with trans O-W-O angles of 168° cis O-W-O angles of 90-91°, and W-O-C angles of 154-159°. W(DMP)4 belongs to the space group P4/n with a = b = 14 475 (2) ?, c = 7.097 (3) ?, V = 1487.0 ?3, and Z = 2. Final R1 = 0.055 and R2 = 0.057. W(DMP)4 contains an essentially planar WO4 core in which trans O-W-O angles are 173.7 (3)°, cis O-W-O angles are 89.8 (2)°, and W-O-C angles are 160.7 (4)°. W(DIPP)4 is too crowded to react with a simple substrate such as an internal acetylene while W(DMP)4 reacts with 3-hexyne to yield W(3-hexyne)(DMP)4, with trimethylsilyl azide to yield W(NSiMe3)(DMP)4, with (SiMe3)CHN2 to yield W[N2CH-(SiMe3)](DMP)4, and with O2, cyclohexene oxide, or iodosylbenzene to yield W(O)(DMP)4. An attempt to replace the DMP ligands by S-2,4,6-R3C6H2 (R = Me or i-Pr) ligands yielded W(S)(DMP)4.
