100207-68-9Relevant articles and documents
Four-coordinate Mo(II) as (silox)2Mo(PMe3) 2 and its W(IV) congener (silox)2HW(η2- CH2PMe2)(PMe3) (silox = tBu 3SiO)
Kuiper, David S.,Wolczanski, Peter T.,Lobkovsky, Emil B.,Cundari, Thomas R.
, p. 10542 - 10553 (2008)
The reduction of [(tBu3SiO)2MoCl] 2 (22) provided the cyclometalated derivative, (silox)2HMoMo(κ-O,C-OSitBu2CMe 2CH2)(silox) (3), and alkylation of 22 with MeMgBr afforded [(tBu3SiO)2MoCH 3]2 (42). The hydrogenation of 42 was ineffective, but the reduction of 22 under H2 generated [(tBu3SiO)2MoH]2 (5 2), and the addition of 2-butyne to 3 gave [(silox) 2Mo]2(μ:η2η2-C 2Me2) (6), thereby implicating the existence of [(silox)2Mo]2 (12). The addition of (silox)H to Mo(NMe2)4 led to (silox)2Mo(NMe 2)2 (7), but further elaboration of the core proved ineffective. The silanolysis of MoCl5 afforded (silox) 2MoCl4 (8) and (silox)3MoCl3 (9) as a mixture from which pure 8 could be isolated, and the addition of THF or PMe3 resulted in derivatives of 9 as (silox)2Cl 3MoL (L = THF, 10; PMe3, 11). Reductions of 11 and (silox)2WCl4 (15) in the presence of excess PMe 3 provided (silox)2Cl2MPMe3 (M = Mo, 12; W, 16) or (silox)2HW(η2-CH2PMe 2)PMe3 (14). While (silox)2W(PMe 3)2 was unstable with respect to W(IV) as 14, a reduction of 12 led to the stable Mo(II) diphosphine, (silox) 2Mo(PMe3)2 (17). X-ray crystal structures of 10 (pseudo-Oh), 12 (square pyramidal), and 14 and 17 (distorted T d) are reported. Calculations address the diamagnetism of 12 and 16, and the distortion of 17 and its stability to cyclometalation in contrast to 14.
PREPARATION OF MOLYBDENUM(IV) COMPLEXES OF SEQUENTIAL POLYPEPTIDES CONSISTING OF GLYCINE AND L-CYSTEINE AND THEIR CATALYTIC ACTIVITY FOR THE ELECTRON TRANSFER REDUCTION OF ACETYLENE IN PROTIC MEDIA.
Oguni,Shimazu,Nakamura
, p. 1 - 8 (1983)
Molybdenum(IV) complexes of sequential polypeptides, (Gly//2Cys)//n and (Gly//3Cys)//m were prepared, and their catalytic activities examined in the electron transfer reduction (by NaBH//4) of acetylene. These molybdenum complexes had excellent catalytic