15096-70-5

Upstream product

• 13939-06-5 molybdenum hexacarbonyl 
• 14971-42-7 triphenylphosphinemolybdenumpentacarbonyl 
• 1184-78-7 trimethylamine-N-oxide 
• 603-35-0 triphenylphosphine 
• 12146-37-1 (bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum⁽⁰⁾ 
• 12089-15-5 tricarbonylmesitylenemolybdenum⁽⁰⁾ 
• 114673-03-9 trans-MoBr₂(CO)2(PPh₃)2 
• 82443-48-9 {Mo(CO)3(P(C₆H₅)3)2(Cl)2} 
• 41792-83-0 isobutylene dianion 
• 15096-70-5 cis-{molybdenum⁽⁰⁾(carbonyl)4(P(phenyl)3)2} 
• 15038-48-9 tris(acetonitrile)tricarbonylmolybdenum⁽⁰⁾ 
• 131242-36-9 2-sulfanylpyrimidine 
• 57298-71-2 cis-[Mo(CO)4(THF)2] 
• 102942-42-7 Mo(CO)4(NHC₅H₁₀)(P(C₆H₅)2P(O)(OC₂H₅)2) 

Downstream Products

• 14971-42-7 triphenylphosphinemolybdenumpentacarbonyl 
• 603-35-0 triphenylphosphine 
• 15096-70-5 trans-Mo(CO)4(PPh₃)2 
• 14285-67-7 MoBr₂(NO)2(P(C₆H₅)3)2 
• 108215-02-7 MoF₂(NO)2(P(C₆H₅)3)2 

Relevant academic research and scientific papers

Activation of the M-CO bond in transition-metal complexes. Fe2(CO)6(SMe)2 and phosphine-substituted derivatives as good catalysts in metal carbonyl substitution reactions

The catalytic activity of Fe2(CO)6(SMe)2 in CO substitution reactions on several transition-metal carbonyl complexes is reported and compared with the results obtained with other reagents. Experimental evidence has been gained to support the view that radical species are involved in these reactions and a possible pathway is proposed to explain the catalytic cycle.

Conformational chiral polymorphism in cis-bis-triphenylphosphine complexes of transition metals

The structure of cis-[Mo(CO)4(PPh3)2] 1 was determined by F. A. Cotton, D. J. Darensbourg, S. Klein and B. W. S. Kolthammer, Inorg. Chem., 1982, 21, 1651-1655, with the space group P1. A second polymorph 2 is reported here, with the space group P21/c. The compounds differ in the interactions between the conformational chiral triphenylphosphine groups. In 1, there is π-π stacking between adjacent phenyl groups, whereas in 2, there are σ-π interactions instead. A search of the Cambridge Structural Database reveals that this is a relatively frequent occurrence in cis-bis-triphenylphosphine complexes and the phenomenon can be analysed by means of the C(ipso)-P-M-P torsion angles. The majority of compounds fall in the π-π stacking data area with torsion angles of 10-15° and 55-60°; however, for octahedrally coordinated metals, the optimum is a σ-π interaction at 40°/40°. This corresponds well to the values in 2: 46°/40°, but for 1, we instead find the torsion angles to be 11°/18°. There is indeed a small occurrence of these values as well in the data, and it appears that for 1, this conformation is stabilised by weak COH-C hydrogen bonds. Density functional theory (DFT) calculations indicate that 1 is the more stable polymorph by 72 kJ mol?1 but that the strain of the complexes (the difference between a relaxed molecule in the respective conformation and the structure in the crystal) is larger for 1 than for 2, further indicating that a special intermolecular interaction is responsible for the stability of this polymorph. In both polymorphs, the triphenylphosphines have the same conformational chirality, consistent with single-molecule calculations that predict racemic conformations to be substantially higher in energy for both σ-π interactions (+17 kJ mol?1) and π-π stacking (+30 kJ mol?1).

Reactivity of [Mo(CO)3(NCMe)3] towards pyrimidine-2-thiol (pymSH) and thiophenol (PhSH) in the presence of phosphine auxiliaries: Synthesis of mono- and dinuclear complexes bearing κ2 and μ,κ2-pymS coordination

The reaction of [Mo(CO)3(NCMe)3] with added thiol in the presence of a phosphine auxiliary has been investigated. Treatment of [Mo(CO)3(NCMe)3] with pyrimidine-2-thiol (pymSH) and PPh3 at 60 °C in MeC

Selective Isomerization of Terminal Alkenes to (Z)-2-Alkenes Catalyzed by an Air-Stable Molybdenum(0) Complex

Positional and stereochemical selectivity in the isomerization of terminal alkenes to internal alkenes is observed using the cis-Mo(CO)4(PPh3)2 precatalyst. A p-toluenesulfonic acid (TsOH) cocatalyst is essential for catalyst activity. Various functionalized terminal alkenes have been converted to the corresponding 2-alkenes, generally favoring the Z isomer with selectivity as high as 8:1 Z:E at high conversion. Interrogation of the catalyst initiation mechanism by 31P NMR reveals that cis-Mo(CO)4(PPh3)2 reacts with TsOH at elevated temperatures to yield a phosphine-ligated Mo hydride (MoH) species. Catalysis may proceed via 2,1-insertion of a terminal alkene into a MoH group and stereoselective β-hydride elimination to yield the (Z)-2-alkene.

An examination of the effects of borate group proximity on phosphine donor power in anionic (phosphino)tetraphenylborate ligands

The ligand electron-donating abilities are compared among a series of monodentate, anionic (phosphino)tetraphenylborate phosphines [Ph4P][Ph2P-R-C6H4BPh3] (R = -C6H4-, -CH2-, -CH2CH2- or none), and their neutral counterparts Ph2PR (R = biphenyl, -CH2Ph, -CH2CH2Ph or Ph). Among the anionic ligands, the position of the tetraphenylborate group relative to the diphenylphosphino donor moiety was systematically varied in an effort to examine how its proximity impacts donor power. The donor power was determined by measuring the 31P-77Se coupling constant for the corresponding selenide of each phosphine ligand via 31P NMR spectroscopy. The anionic ligands yield lower 31P-77Se coupling constants than those measured for their respective neutral counterparts. Moreover, the 31P-77Se coupling constants among the anionic ligands increase when the tetraphenylborate group is positioned further from the phosphorus centre.

Rapid synthesis of Group VI carbonyl complexes by coupling borohydride catalysis and microwave heating

Several Group VI tetracarbonyl phosphine and tertiary amine complexes [M(CO)4 L2, M = Cr, Mo, W, L2 = 2PPh 3, dppm, dppe, dppp, dppb, bpy, phen, dppf] were synthesized in minutes in the microwave at moderate temperature, atmospheric pressure, and utilizing NaBH4 as a catalyst. The reactions were optimized by careful solvent selection. The octahedral complexes were isolated in percent yields ranging from 17 to 95. The lower temperatures, shorter reaction times, benign solvents, and lower pressures as compared to the traditional thermal syntheses provide a rapid, eco-friendly synthetic route to these common Group VI complexes.

Organometallic chemistry in a conventional microwave oven: The facile synthesis of group 6 carbonyl complexes

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.

The nucleophilic addition of alpha-metallated 1,3-dioxanes to planar chiral cationic eta3-allylmolybdenum complexes. Synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid methyl ester, a key component of the Cryptophycins.

Two adjacent stereogenic centres and a pendant alkene were constructed via nucleophilic addition of a 1,3-dioxan-4-ylcopper(I) reagent to a cationic eta3-allylmolybdenum complex as part of a synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid, a key component of the Cryptophycins. Oxidative addition of Mo(CO)(4)(THF)(2) to allyl benzoates provides an efficient synthesis of eta3-allylmolybdenum(dicarbonyl) complexes.

Stereochemical nonrigidity in heterobimetallic complexes containing the bent metallocene-thiolate fragment

The physical properties and reactions of Cp2Ti(S-p-C6H4X)2 (1) and Cp2Ti(μ-S-p-C6H4X)2Mo(CO) 4 (2) (X = Cl, H, CH3, OCH3) complexes as well as the mechanism of the Cp site equilibration process in bimetallic complexes were investigated. Cyclic voltammographs recorded in CH2Cl2 showed two reversible waves for Ti(IV) ? Ti(III) and Mo(0) ? Mo(I) processes in 2 and one reversible wave for Ti(IV) ? Ti(III) in 1. Positions of these waves varied uniformly with the Hammett σ parameter of the X substituent. Variable-temperature 1H NMR studies provided values for ΔG? of the Cp equilibration process which are ca. 30 kJ/mol smaller than ΔG? for Cp2Ti(S-p-C6H4X)2 displacement from 2 by CO. This indicates that the fluxional process in 2 does not occur through a ligand dissociation process and argues for a mechanism of pyramidal inversion on sulfur. The X-ray structure for Cp2Ti(μ-S-p-C6H4Cl)2Mo(CO) 4 (2a) is reported. Complex 2a crystallizes in the monoclinic space group P21/n, with a = 12.396 (7) A?, b = 16.78 (2) A?, c = 12.838 (9) A?, β = 94.29 (5)°, Z = 4, and V = 2662 (3) A?3. The Ti atom is in pseudotetrahedral coordination environment whereas the Mo is octahedrally coordinated. The S1-Ti-S2 and S1-Mo-S2 angles are obtuse (100.8 (1) and 97.6 (1)°, respectively) and Ti-S-Mo angles are acute (80.8 (1)°) in the planar Ti-S2-Mo ring, supportive of metal-metal interactions implied by spectroscopic and electrochemical data. The phenyl groups are in an anti arrangement with respect to the Ti-S2-Mo plane.

Syntheses and structure of pseudooctahedral molybdenum-η3-hexadienyl complexes

Compounds of the type 3-C5H6Me)(CO)2(MeCN)2> where X = Cl (1) and Br (2) have been prepared by oxidative addition of 1-halohexa-2,4-dienes to Mo(CO)3(MeCN)3.Addition of the bisphosphine Ph2PCH2CH2PPh2 (dppe) or 2,2'-bipyridine (bipy) to 2 gives 3-C5H6Me)(CO)2(dppe)> (3) or 3-C5H6Me)(CO)2(bipy)> 1/2MeCN (4), respectively, in high yields. 1,10'-phenanthroline and 1 afforded the bright red complex 3-C5H6Me)(CO)2(phen)> (5).A crystallographic X-ray analysis showed the structure of 2 to be analogous to diether and diamine chelatespreviously reported.According to spectroscopic data the bisphosphine compound 3 adopts a different structure than 2.