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Preparation and characterization of binuclear complexes of molybdenum(III) and molybdenum(V) via oxidative decarbonylation

Preparation and characterization of binuclear complexes of molybdenum(III) and molybdenum(V) via oxidative decarbonylation. Reactions of LMo(CO)3 (L = 1,5,9-triazacyclododecane) and crystal structure of anti-[L2Mo2O4](ClO4)2.2H2O. Wieghardt, Karl; Guttmann, Martina; Chaudhuri, Phalguni; Gebert, Walter; Minelli, Martin; Young, Charles G.; Enemark, John H. (Lehrst. Anorg. Chem. I, Ruhr-Univ., Bochum D-4630, Fed. Rep. Ger.). Inorg. Chem., 24(20), 3151-5 (English) 1985. CODEN: INOCAJ. ISSN: 0020-1669. DOCUMENT TYPE: Journal CA Section: 78 (Inorganic Chemicals and Reactions) Section cross-reference(s): 67, 75 1,5,9-Triazacyclododecane (L) reacts with Mo(CO)6 in decalin at 150° to yield yellow, air-stable LMo(CO)3 (I). Oxidn. of I with Br, HNO2 (or NOBF4), or HCl in the presence of O gave [LMo(CO)3Br](Br3), [LMo(CO)2NO]BF4, and LMoCl3, resp. Oxidative decarbonylation of I in HClO4 with O gives the 2 isomers purple anti-[L2Mo2O4](ClO4)2.2H2O (II) and yellow syn-[L2MoO4(ClO4)2].H2O (III). Redn. of II with Zn amalgam in aq. soln. in the presence and absence of coordinating acids (HBF4, HCO2H, HOAc, HCl) affords diamagnetic, green [L2Mo2(m-OH)2(OH)2]I2.2H2O, [L2Mo2(m-OH)2(m-HCO2)]I3×2H2O, [L2Mo2(m-OH)2(m-OAc)]I3, and [L2Mo2(m-OH)2Cl2](ClO4)2. II crystallizes in the monoclinic space group P21/c with a 8.515(8), b 11.11(2), c = 16.56(3) ?, b 92.3(1)°, d.(calcd.) = 1.77 g/cm3 for Z = 2, and R = 0.039 and Rw = 0.045 for 3216 observations. The structure consists of dimeric cations with an anti-dioxobis(m-oxo)dimolybdenum(V) core (edge-sharing octahedra); the short Mo-Mo distance of 2.586(1) ? and the diamagnetism of II indicate a Mo-Mo single bond. The 4-membered Mo2O2 ring is planar. In alk. aq. solns. II isomerizes irreversibly to III. The kinetics of this reaction were measured, and a possible mechanism is discussed. This isomerization was also demonstrated by 95Mo NMR spectroscopy.

New synthetic routes to macrocyclic triamines

New synthetic routes to macrocyclic triamines. Alder, Roger W.; Mowlam, Rodney W.; Vachon, David J.; Weisman, Gary R. (Sch. Chem., Univ.Some commonly used reagents like 139258-68-7 and 64924-82-9 are used in this experiment. Bristol, Bristol BS8 1TS, UK). J. Chem. Soc., Chem. Commun., (6), 507-8 (English) 1992. CODEN: JCCCAT. ISSN: 0022-4936. DOCUMENT TYPE: Journal CA Section: 28 (Heterocyclic Compounds (More Than One Hetero Atom)) 1,5,9-Triazacyclododecane I (R = R1 = H) and related macrocyclic triamines can be conveniently constructed around a single carbon atom as template; this route permits the prepn. of selectively alkylated derivs. Thus, the reaction of bicyclic guanidine II with 1,3-dibromopropane, followed by redn. of the tricyclic guanidinium salt with LiAlH4 gave orthoamide III. Acid-catalyzed hydrolysis of III gave I (R = R1 = H). Methylation of III with MeI, followed by base-catalyzed hydrolysis gave III (R = Me, R1 = H). Methylation of III with MeI, followed by NaBH4 redn. gave III ( R = R1 = Me). .