17731-95-2

Upstream product

• 205106-36-1 Mo(CO)3(1,3,5-trimethyl-1,3,5-triazacyclohexane) 
• 75-05-8 acetonitrile 
• 12176-06-6 hydrido(tricarbonyl)(cyclopentadienyl)molybdenum 
• 78353-19-2 (η5-C5H4Me)Mo(CO)3H 
• 868831-93-0 [Mo(CO)3(η5-(2-(dimethylammonium)ethyl)cyclopentadienyl)] 
• 223732-96-5 (η(3)-tris[(methylthio)methyl]silane)Mo(CO)3 
• 168842-67-9 [Mo(η(5)-C5H5)(CO)3(C10H7Ph2)] 
• 126191-01-3 Mo(CO)3(η3-tris(2,4,6-trimethyloxyphenyl)phosphine) 
• 13939-06-5 molybdenum hexacarbonyl 
• 1239212-60-2 [Mo(carbonyl)3(1,3,5-tris(thiocyanatomethyl)mesitylene)] 

Downstream Products

• 56009-06-4 {Mo(CO)3NCCH₃P(C₆H₅)2CH₂P(C₆H₅)2} 
• 135740-73-7 monoacetonitrile(triphenylphosphiniminequinoline) tricarbonylmolybdenum 
• 1200401-27-9 fac-[Mo(CO)3(NCMe)((Ph₂P)2C=C=N-t-Bu)] 
• 137370-94-6 Mo(CO)3(NCCH₃)2(SnCl(C₆H₅)2)Cl 
• 153956-41-3 [Mo(CO)3CH₃C(CH₂P(C₂H₅)(C₆H₅))3] 
• 93976-40-0 tricarbonyl(N,N,N',N'-tetraethyldithiooxamide)(triphenylphosphine)molybdenum 
• 93976-39-7 tricarbonyl(N,N,N',N'-tetramethyldithiooxamide)(triphenylphosphine)molybdenum 
• 261773-26-6 fac-Mo(CO)3(1,2-bis(diphenylphosphino)benzene)(CH₃CN) 
• 319016-48-3 fac-(CO)3Mo(CH₃CN)(1,1'-diphenylphosphinoferrocene) 
• 203342-21-6 [Mo(CO)4(Mo(CO)2(η4-P3CtBu)(η4-P2(CtBu)2))] 

Relevant academic research and scientific papers

On the coordination chemistry of corannulene, the smallest "buckybowl"

A variety of methods, conventional and non-conventional, are used in attempts to prepare the compounds (η6-corannulene)M(CO) 3 (M = Cr, Mo, W), all unsuccessful. Conventional methods are also utilized in attempts to prepare the compound [CpFe(η6- corannulene)]PF6, but these result in mixtures of cationic CpFe(arene) complexes containing partially hydrogenated corannulene; similar results have been reported for other polyaromatic hydrocarbons. DFT calculations on the compound (η6-corannulene)Cr(CO)3 suggest that the (η6-corannulene)-Cr linkage is only a few kcal/mol weaker than the corresponding bond in (η6-benzene)Cr(CO)3, implying that failures in syntheses arise from kinetic, not thermodynamic problems.

Carborane Stabilized 19-Electron Molybdenum Metalloradical

Paramagnetic metal complexes gained a lot of attention due to their participation in a number of important chemical reactions. In most cases, these complexes are dominated by 17-e metalloradicals that are associatively activated with highly reactive paramagnetic 19-e species. Molybdenum paramagnetic complexes are among the most investigated ones. While some examples of persistent 17-e Mo-centered radicals have been reported, in contrast, 19-e Mo-centered radicals are illusive species and as such could rarely be detected. In this work, the photodissociation of the [Cp(CO)3Mo]2 dimer (1) in the presence of phosphines was revisited. As a result, the first persistent, formally 19-e Mo radical with significant electron density on the Mo center (22%), Cp(CO)3Mo·PPh2(o-C2B10H11) (5b), was generated and characterized by EPR spectroscopy and MS as well as studied by DFT calculations. The stabilization of 5b was likely achieved due to a unique electron-withdrawing effect of the o-carboranyl substituent at the phosphorus center.

Aryl Oligogermanes as Ligands for Transition Metal Complexes

The ligand properties of a series of aryl oligogermanes R3Ge-GeAr3, 3–7 [Me3Ge-GePh3 (3), Me3Ge-Ge(pTol)3 (4), Ph3Ge-GePh3 (5), (C6F5)3Ge-GePh3 (6), Ph3Ge-GeMe2GePh3 (7)] for the synthesis of transition metal carbonyl complexes such as R3Ge-GeAr2(R′C6H4-η6)M(CO)3 (M = Cr, 3a–7a; M = Mo, 3b; M = W, 3c) were investigated. The target complexes were obtained in moderate yields using several different synthetic approaches. The physicochemical properties of these new derivatives were investigated by IR, UV/Vis, NMR spectroscopy, electrochemistry, and DFT calculations. The molecular structures of 3c, 4a, and 5a were studied by single-crystal X-ray diffraction analysis. A comparative analysis of donor and acceptor properties of aryl oligogermanes as ligands for transition metal carbonyl complexes is reported.

Reactions of tetracyclone molybdenum complexes with electrophilic alkynes: Cyclopentadienone-alkyne coupling and alkyne coordination

The reactions of the complexes [Mo(CO)2(4-C4Ph4CO)2] and [Mo(CO)3(NCMe)(4-C4Ph4CO)] with the alkynes dimethyl acetylenedicarboxylate (DMAD; RC - CR where R = CO2Me) and methyl propiolate (RC - CH) have been studied. In the case of DMAD, the initial product is the green carbonyl complex [Mo(CO)(RC - CR)(5,σ-C4Ph4COCR - CR)] (3), in which two alkyne molecules have been incorporated: one is linked to the carbonyl group of the tetracyclone ligand, whereas the other is -bound to the metal as a four-electron donor. Oxidation of this compound affords yellow [Mo(O)(RC - CR)(5,σ-C4Ph4COCR - CR)] (8). When the -acceptor carbonyl ligand is replaced by the-donor oxo group, the alkyne ligand changes orientation: it lies parallel to the Mo-CO bond in 3 but perpendicular to the Mo - O group in 8. Analogous complexes (9, 10) were isolated in the case of methyl propiolate; each exists as a mixture of two isomers depending on the orientation of the unsymmetrical alkyne ligand.

Synthesis of a carbon analogue of scytonemin

The synthesis of a carbon analogue of scytonemin was accomplished on the basis of molybdenum-mediated intramolecular double Pauson-Khand type reaction of bis(allenyne), followed by the double aldol condensation of the formed double Pauson-Khand type adduct.

Carbon monoxide releasing molecules and uses thereof

Provided herein are novel carbon-monoxide releasing molecules (CO-RMs) of the Formula (I): and esters, amides, salts, solvates and hydrates thereof; wherein R1 and R2 are as described herein. Also provided are pharmaceutical compositions comprising these compounds, methods of their preparation, and their use in the treatment of liver disease and inflammation.

Synthetic, structural, NMR, and computational study of a geminally bis(peri-substituted) tridentate phosphine and its chalcogenides and transition-metal complexes

Coupling of two acenaphthene backbones through a phosphorus atom in a geminal fashion gives the first geminally bis(peri-substituted) tridentate phosphine 1. The rigid nature of the aromatic backbone and overall crowding of the molecule result in a rather inflexible ligand, with the three phosphorus atoms forming a relatively compact triangular cluster. Phosphine 1 displays restricted dynamics on an NMR time scale, which leads to the anisochronicity of all three phosphorus nuclei at low temperatures. Strained bis- and tris(sulfides) 2 and 3 and the bis(selenide) 4 have been isolated from the reaction of 1 with sulfur and selenium, respectively. These chalcogeno derivatives display pronounced in-plane and out-of-plane distortions of the aromatic backbones, indicating the limits of their angular distortions. In addition, we report metal complexes with tetrahedral [(1)Cu(MeCN)][BF 4] (5), square planar [(1)PtCl][Cl] (6), trigonal bipyramidal [(1)FeCl2] (7), and octahedral fac-[(1)Mo(CO)3] (8) geometries. In all of these complexes the tris(phosphine) backbone is distorted, however to a significantly smaller extent than that in the mentioned chalcogenides 2-4. Complexes 5 and 8 show fluxionality in 31P and 1H NMR. All new compounds 1-8 were fully characterized, and their crystal structures are reported. Conclusions from dynamic NMR observations were augmented by DFT calculations.

Synthesis and characterization of hydrido carbonyl molybdenum and tungsten PNP pincer complexes

In the present study the Mo(0) and W(0) complexes [M(PNP)(CO)3] as well as seven-coordinate cationic hydridocarbonyl Mo(II) and W(II) complexes of the type [M(PNP)(CO)3H]+, featuring PNP pincer ligands based on 2,6-diaminopyridine, have been prepared and fully characterized. The synthesis of Mo(0) complexes [Mo(PNP)(CO)3] was accomplished by treatment of [Mo(CO)3(CH3CN)3] with the respective PNP ligands. The analogous W(0) complexes were prepared by reduction of the bromocarbonyl complexes [W(PNP)(CO)3Br]+ with NaHg. These intermediates were obtained from the known dinuclear complex [W(CO) 4(μ-Br)Br]2, prepared in situ from W(CO)6 and stoichiometric amounts of Br2. Addition of HBF4 to [M(PNP)(CO)3] resulted in clean protonation at the molybdenum and tungsten centers to generate the Mo(II) and W(II) hydride complexes [M(PNP)(CO)3H]+. The protonation is fully reversible, and upon addition of NEt3 as base the Mo(0) and W(0) complexes [M(PNP)(CO)3] are regenerated quantitatively. All heptacoordinate complexes exhibit fluxional behavior in solution. The mechanism of the dynamic process of the hydrido carbonyl complexes was investigated by means of DFT calculations, revealing that it occurs in a single step. The structures of representative complexes were determined by X-ray single-crystal analyses.

1,3,5-Tris(thiocyanatomethyl)mesitylene as a Ligand. Pseudooctahedral molybdenum, manganese, and rhenium carbonyl complexes and copper and silver dimers. Copper-catalyzed carbene- and nitrene-transfer reactions

New molybdenum(0), molybdenum(II), manganese(I), rhenium(I), silver(I), and copper(I) complexes with the 1,3,5-tris(thiocyanatomethyl)mesitylene [Ms(CH2SCN)3] ligand have been synthesized and characterized by IR, NMR, and by X-ray diffraction (except for the rhenium complex). The Ms(CH2SCN)3 ligand coordinated with the molybdenum, manganese, and rhenium carbonyl fragments as a tripodal chelate. With copper and silver, dimeric dicationic species were obtained instead, with the Ms(CH2SCN)3 ligand acting simultaneously as a bidentate chelate and bridge. The [{Cu(Ms(CH2SCN)3)} 2][BAr′4]2 (BAr′4 = tetra(3,5-bis(trifluoromethyl)phenyl)borate) product is an excellent catalyst for cyclopropanation and aziridination of alkenes and cyclopropenation of alkynes by means of carbene- and nitrene-transfer reactions.

(2-(Dimethylammonium)ethyl)cyclopentadienyltricarbonyl-metalates: Group VI metal zwitterions. Attenuation of the bronsted basicity and nucleophilicity of formally anionic metal centers

Protonation of (2-(dimethylamino)ethyl)cyclopentadienyl (CpN) group VI metal carbonyl anions with acetic acid proceeds at the amine to provide zwitterionic (2-(dimethylammonium)- ethyl)cyclopentadienyltricarbonylmetalates, M(CO)3(η5-CpNH) (M = Cr (1), Mo (2), W (3)). Few zwitterionic organometalates with anionic metal centers and positive charges that cannot be delocalized have been reported to date. The impact of the intramolecular charge separation on the structures and reactivity of zwitterionic organometalates is of current interest. The M(CO)3 units of structurally characterized 1-3 are significantly perturbed in solution and the solid state due to ion-pairing between the pendant ammonium cation and anionic metal center. The concentration and solvent dependence of the 1H NMR ammonium hydrogen chemical shifts of 1-3 and the intramolecular N...M separations of these zwitterions in the solid state are consistent with three-center-four-electron N - H...M hydrogen bonding. One other hydrogen bond with a zerovalent group VI metal acceptor has been characterized to date. The intramolecular charge separation attenuates the reactivity of the anionic metal centers of 1-3 relative to that of [M(CO) 3(η5-Cp)]-. Structurally characterized [WH(CO)3- (η5-CpNH)]Cl (4) was the only isolable salt obtained from protonation of 1-3; the Cr and Mo analogues are unstable relative to 1 and 2, respectively. Structurally characterized [M(AuPPh3)(CO)3(η5-CpNH)]Cl (M = Mo (5), W(6)) were synthesized via reactions of 2 and 3, respectively, with Ph3PAuCl and protonation of M(AuPPh3)(CO) 3(η5-CpN) (M = Mo (8), W (9)) with HCl. Pure samples of the analogous chromium salt were inaccessible from either 1 or structurally characterized Cr(AuPPh3)(CO)3(η 5-CpN) (7).