65337-26-0Relevant articles and documents
CARBON MONOXIDE RELEASING MOLECULES
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Paragraph 0264; 0406-0407, (2018/10/19)
Disclosed are carbon monoxide releasing complexes comprising a transition metal, at least one carbon monoxide ligand, and a pH responsive ligand that modulates the release of carbon monoxide, compositions comprising such complexes, and methods of using such compounds for treating various diseases and conditions and preserving cells, tissue or organs for transplantation.
Supramolecular Arrangement of Molybdenum Carbonyl Metallosurfactants with CO-Releasing Properties
Parera, Elisabet,Marín-García, Maribel,Pons, Ramon,Comelles, Francesc,Suades, Joan,Barnadas-Rodríguez, Ramon
, p. 484 - 493 (2016/03/01)
Two families of molybdenum carbonyl metallosurfactants, Mo(CO)5L and Mo(CO)4L2, were synthesized using the functionalized phosphines Ph2P(CH2)nSO3Na (n = 2, 6, 10) and characterized by the usual spectroscopic and spectrometric methods. The study of the supramolecular arrangements of these compounds in aqueous medium has been performed by surface tension, fluorescence, dynamic light scattering, cryo-TEM, and small-angle X-ray scattering. All data point to the formation of medium and large vesicular structures with a membrane similar to the classical lipid bilayer, but it contains organometallic fragments instead of simple hydrophobic chains. Studies of CO release with these molybdenum carbonyl metallosurfactants have shown their viability as promising CO-releasing molecules.
Organometallic chemistry in a conventional microwave oven: The facile synthesis of group 6 carbonyl complexes
Ardon, Michael,Hogarth, Graeme,Oscroft, Daniel T.W.
, p. 2429 - 2435 (2007/10/03)
Syntheses proceeding by reflux may be improved, accelerated and simplified, by carrying out the reaction in a modified conventional microwave oven. To demonstrate the potential of this method, the synthesis of over 20 group 6 organometallic compounds is reported. Hexacarbonyls, most notably Mo(CO)6, react with a range of mono, and bi, and tridentate ligands in a modified conventional microwave oven. They generally proceed without an inert atmosphere, yields are high and reaction times are short. For example, cis -[Mo(CO)4(dppe)] is prepared in >95% yield in 20 min. Reaction of Mo(CO)6 with dicyclopentadiene affords a simple one-step synthesis of [CpMo(CO)3]2 in >90% yield, which reacts further with alkynes in toluene to produce dimetallatetrahedrane derivatives, [Cp2Mo2(CO)4 (μ-RC2R)]; presumably via the in situ formation of air-sensitive [CpMo(CO)2]2. Dimolybdenum tetra-acetate is also prepared in 48% yield in 45 min, however, this reaction requires an inert atmosphere. While W(CO)6 reacts rapidly with amines to give cis diamine adducts in high yields, direct reactions with phosphines are not so clean. Bis(phosphine) complexes are, however, cleanly formed when a small amount of piperidine is added to the reaction mixture, presumably via the bis(piperidine) complex cis-[W(CO)4(pip)2]. Reactions with Cr(CO)6 generally require an inert atmosphere and proceed less cleanly, although the important synthon [Cr(CO)5 Cl][NEt4] was prepared in 30 min (74% yield), while [(η6-C6H5OMe)Cr(CO)3] can be prepared in 45% after 4 h.
Direct photolytic route to trans-Cr(CO)4(AsPh3)2 and crystal structures of cis-Mo(CO)4(AsPh3)2 and cis-W(CO)4(AsPh3)2
Bergstrom, Christina L.,Luck, Rudy L.
, p. 77 - 83 (2008/10/08)
The preparation of trans-Cr(CO)4(AsPh3)2 is accomplished in reasonable yield by the direct photolysis of a solution of Cr(CO)6 and an excess of AsPh3 in heptane. The structures of cis-Mo(CO)4(AsPh3)2 and cis-W(CO)4(AsPh3)2 are reported. These are found to be isostructural and consist of distorted octahedral geometries with As-M-As angles of 102.56(2) and 102.62(2)° for M = Mo and W, respectively. The Mo-As distances of 2.6428(9) and 2.6489(9) A? are significantly longer than those in the W analogue at 2.6384(6) and 2.6361(6) A?. On the basis of a comparison to literature data, the AsPh3 ligands in these molecules can be described as extremely compressed.
Ligand effects in the substitution chemistry of cis-bis(piperidine)tetracarbonylmolybdenum(0). A molybdenum-95 NMR study
Malito, John,Alyea, Elmer C.,Gossage, Robert A.
, p. 873 - 878 (2007/10/02)
Molybdenum-95 NMR chemical shifts are reported for a series of Mo(0) compounds of the type Mo(CO)4(pip)2-nLn (n=1,2; L=substituted pyridine ligands).The δ(95Mo) values correlate well with the pKa values for the substituted pyridines; for the n=1 series, Δ(95Mo) ranges from -1053 ppm (pKa=1.86 for 4-CN) to -1120 ppm (pKa=9.61 for 4-NMe2).The effects of solvent polarity and some in situ reactivity studies are described and the nature of the Mo-L bond compared to that with piperidine and some other ligands is discussed.
Transition-metal Chemical Shifts in Complexes of Molybdenum(0) and Tungsten(0)
Andrews, Geoffrey T.,Colquhoun, Ian J.,McFarlane, William,Grim, Samuel O.
, p. 2353 - 2358 (2007/10/02)
Molybdenum-95 and tungsten-183 n.m.r. spectra have been measured by direct observation and by multiple-resonance methods respectively for 65 related derivatives of and with (mainly) phosphorus ligands.The chemical shifts of the two nuclei are remarkably parallel, those for (183)W being ca. 1.7 times more sensitive to changes in chemical environment than those for (95)Mo.The chemical shifts are temperature-dependent, and trends in them can be largely accounted for by variations in the mean electronic excitation energy.The metal-phosphorus spin-coupling constants are very predictable.Molybdenum-95 linewidths in many cases are quite small, and can be broadly explained by the use of a point-charge model.
X-ray structural studies of cis-Mo(CO)4(PR3)2 (R = Me, Et, n-Bu) derivatives and their relationship to solution isomerization processes in these octahedral species
Cotton, F. Albert,Darensbourg, Donald J.,Klein,Kolthammer, Brian W. S.
, p. 2661 - 2666 (2008/10/08)
The crystal and molecular structures of cis-Mo(CO)4(PMe3)2 (1), cis-Mo(CO)4(PEt3)2 (2), and cis-Mo(CO)4[P(n-Bu)3]2 (3) have been determined for the purpose of seeking correlations between structural features - especially evidence of intramolecular strain - and reactivity. The main results are as follows. 1: space group P21/n, with unit cell dimensions of a = 9.770 (1) ?, b = 12.109 (1) ?, c = 14.183 (1) ?, β = 95.435 (7)°, V = 1670.5 (5) ?3, and Z = 4. The Mo-P distances average 2.522 (1) ?, and ∠P-Mo-P = 97.54 (4)°. 2: space group P21/c, with unit cell dimensions of a = 9.740 (3) ?, b = 16.399 (1) ?, c = 14.601 (2) ?, β = 109.49 (2)°, V= 2199 (1) ?3, and Z = 4. The Mo-P distances average 2.544 (4) ?, and ∠P-Mo-P = 100.27 (3)°. 3: space group P21/c, with unit cell dimensions of a = 20.27 (1) ?, b = 9.442 (3) ?, c = 19.011 (6) ?, β = 107.59 (3)°, V = 3468 (4) ?3, and Z = 4. The Mo-P distances average 2.552 (8) ?, and ∠P-Mo-P = 99.29 (4)°. Within this set of three compounds, there is a fairly good correlation of both steric strain, as evidenced by the P-Mo-P angles, and tendency to isomerize to the trans structure with the steric bulk of the PR3 ligands as indicated by cone angles. However, comparison of structural variations in a total of seven cis-Mo(CO)4(PR3)2 compounds shows that more subtle factors are also at work.
