14971-42-7Relevant academic research and scientific papers
Real-time monitoring of microwave-promoted organometallic ligand-substitution reactions using in situ Raman spectroscopy
Barnard, Thomas M.,Leadbeater, Nicholas E.
, p. 3615 - 3616 (2006)
An apparatus has been developed for real-time monitoring of organometallic reactions under microwave irradiation using in situ Raman spectroscopy and its application for monitoring ligand substitution reactions of Mo(CO)6 demonstrated. The Roya
Oxidatively induced one-electron reductive elimination of pentafluorophenyl from [Mo(C6F5)(CO)5]-
Kim, Jungsook,Gipson, Stephen L.
, p. 1371 - 1374 (2004)
The anionic molybdenum(0) complex [Mo(C6F5)(CO) 5]- displays a one-electron oxidation by cyclic voltammetry that is only partially chemically reversible. The partial chemical reversibility is caused by a slow chemical reaction following oxidation. This reaction has been shown to be cleavage of the Mo-C6F5 bond in a one-electron reductive elimination process. Chemical oxidation by ferrocenium in the presence of nucleophiles yields known Mo(CO)5L (L=Py, PPh3) complexes, while oxidation with tropylium traps the C6F5 radical as C7H7C 6F5. NMR and mass spectrometry were used to identify the oxidation products. Simulated cyclic voltammograms have been used to estimate the rate constant for cleavage of the Mo-C6F5 bond in the presence of pyridine as approximately 700 M-1s-1.
Rearrangement of metallabenzynes to chlorocyclopentadienyl complexes
Chen, Jiangxi,Lee, Ka-Ho,Wen, Tingbin,Gao, Feng,Sung, Herman H. Y.,Williams, Ian D.,Lin, Zhenyang,Jia, Guochen
, p. 890 - 896 (2015)
Treatment of the osmabenzyne complex Os{≡C-C(SiMe3)=C(CH3)-C(SiMe3)=CH-}Cl2(PPh3)2 with Mo(CO)6 in refluxing benzene produced the η5-chlorocyclopentadienyl complex Os{
The insertion of terminal phosphinidene complexes into the B-H bond of amine and phosphine boranes
Tian, Rongqiang,Mathey, Fran?ois
, p. 11210 - 11213 (2012)
Push-pull complexation: Transient terminal phosphinidene complexes [RP-W(CO)5] insert at 110 °C into the B-H bonds of L-BH 3 (L = Et3N, Ph3P; see scheme). The reaction is probably driven by an interaction betwee
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.
Synthesis and structure of heterobimetallic compounds with a single thiolato-bridged ligand
Hossain, Md. Munkir,Lin, Hsiu-Mei,Shyu, Shin-Guang
, p. 2655 - 2659 (2007/10/03)
Reactions between CpFe(CO)2SPh and M(CO)5THF (M = Cr, Mo, and W) in a mixture of benzene and THF at room temperature afforded compounds of the type CpFe(CO)2(μ-SPh)M(CO)5 (1) [M = Cr (1a), Mo (1b), and W (1c)] in high yield. However, migration of the thiolato ligand occurred during reactions between CpM(CO)xSPh (M = Fe, x = 2; M = Mo and W, x = 3) and Fe2(CO)9 forming compounds [Fe(μ-SPh)(CO)3]2 and [CpM(CO)x]2 (M = Fe, x = 2; M = Mo and W, x = 3). Single-crystal X-ray diffraction analyses reveal that 1c is a single thiolato-bridged hererobimetallic compound without a metal-metal bond. Metal-metal bond formation in compounds 1 by decarbonylation under thermal or photolytic condition was not observed. Reactions between compounds 1 and PPh3 produced CpFe(CO)2SPh and PPh3M(CO)5 (M = Cr, Mo, and W) by M-S bond cleavage in 1.
31p chemical shift anisotropies of trimethyl- and triphenylphosphine- substituted group 6 metal pentacarbonyl complexes
Wosnick, Jordan H.,Morin, Frederick G.,Gilson, Denis F.R.
, p. 1280 - 1283 (2007/10/03)
The 31P chemical shift tensor components and anisotropies of the trimethyl- and triphenylphosphine complexes of the group 6 metal pentacarbonyls, M(CO)5PR3 (M = Cr, Mo, W and R = Me, Ph), have been measured using solid-sta
Hydroxylamines as new decarbonylating reagents in the synthesis of metal carbonyl derivatives
Maksakov, V. A.,Ershova, V. A.
, p. 69 - 78 (2007/10/02)
Mononuclear and cluster carbonyl complexes react with amino functional compounds under mild conditions in the presence of H2O2 to form mixed amino carbonyl derivatives.It was found that a group of reactive species facilitating the process are hydroxylamines which arise in situ as a result of oxidation of amino compounds.On the basis of kinetic data and certain other measurements the mechanism of interaction of M(CO)6 (M = Cr, Mo, W) and NH2OH is proposed.This includes nucleophilic attack by NH2OH on a carbonyl carbon resulting in CO oxidation and CO2 elimination with simultaneous intramolecular movement of the amino group to the metal atom.The above mechanism is compared with that for the analogous reaction facilitated by Me3NO, studied earlier. Keywords: Chromium; Molybdenum; Tungsten; Osmium; Cluster; Hydroxylamine
Synthesis and Characterization of the Tetrahedranes 3P (M = Mo, W) and Their Derivatives 3P-Mo(CO)5 and 3P-W(CO)5
Kilthau, Thomas,Nuber, Bernd,Ziegler, Manfred L.
, p. 197 - 200 (2007/10/02)
The reaction of Na (M = Mo, W) with PCl3 in diglyme yields the cluster compounds 3P-Mo(CO)5 (2a) and 3P-W(CO)5 (2b) in good yields as well as the tetrahedranes 3P (3a) and 3P (3b) as side products.Compounds 3a, b are obtained independently by the reaction of 2a, b with PPh3.The clusters 2a, b and 3a, b were characterized spectroscopically (IR, NMR, MS) and X-ray structure determinations were carried out on 2a, b. - Key Words: μ3-Phosphorus-trimolybdenum tetrahedrane/ μ3-Phosphorus-tritungsten tetrahedrane
Synthesis, structure, fluxional behavior, and addition reaction of the metal-metal-bonded heterobimetallic phosphido-bridged complex CpW(CO)2(μ-PPh2)Mo(CO)5
Shyu, Shin-Guang,Hsu, Jiun-Yi,Lin, Pei-Jung,Wu, Wen-Jin,Peng, Shie-Ming,Lee, Gene-Hsiang,Wen, Yuh-Shang
, p. 1699 - 1710 (2008/10/08)
The heterobimetallic phosphido-bridged complex CpW(CO)2(μ-PPh2)Mo(CO)5 (1) was prepared by the reaction of CpW(CO)3PPh2 with Mo(CO)4(C7H8). Treatment of 1 with CO produced CpW(CO)3(μ-PPh2)Mo(CO)5 (2). The structures of 1 and 2 were determined by single-crystal X-ray diffraction. Crystal data for 1: C24H15MoO7PW, space group P21/n, a = 14.464(7) A?, b = 11.6743(12) A?, c = 14.7639(14) A?, β = 97.916(12)°, V = 2469.3(6) A?3, Z = 4. The structure was refined to R = 0.054 and Rw = 0.055. Crystal data for 2: C25H15MoO8PW, space group P21/n, a = 9.6322(16) A?, b = 12.4673(21) A?, c = 20.813(3) A?, β = 94.476(12)°, V = 2472.7(7) A?3, Z = 4. The structure was refined to R = 0.035 and Rw = 0.044. The W-Mo distance was 3.2056(16) A? in 1, indicative of a W-Mo bond. The long distance between W and Mo (4.5192(14) A?) in 2 indicates that no metal-metal bond exists in the complex. Fluxional behavior involving the exchange of four Mo CO ligands cis to the phosphido bridge in 1 was studied by variable-temperature 13C NMR spectroscopy. Addition reactions between 1 and Lewis bases L (L = PPh2H, PMe3, P(OMe)3) produced CpW(CO)3(μ-PPh2)Mo(CO)4(L) (3) with L regiospecifically and stereospecifically coordinating to the Mo cis to the phosphido bridge. The structure of CpW(CO)3(μ-PPh2)Mo(CO)4(PMe3) (3a) was determined by single-crystal X-ray diffraction. Crystal data for 3a: C27H24MoO7P2W, space group P21/n, a = 11.756(4) A?, b = 16.423(6) A?, c = 14.968(3) A?, β = 98.397(20)°, V = 2858.8(14) A?3, Z = 4. The structure was refined to R = 0.026 and Rw = 0.031. Reaction of 1 with PPh3 produced CpW(CO)2(μ-PPh2)Mo(CO)4(PPh3) with a metal-metal bond and with PPh3 occupying the position trans to the phosphido bridge. Complexes with similar structures were synthesized by removal of one CO from 3 to regenerate the metal-metal bond to produce CpW(CO)2(μ-PPh2)Mo(CO)4L (4; L = PPh2H, PMe3, P(OMe)3), in which L regiospecifically and stereospecifically coordinates to the Mo and is trans to the phosphido bridge.
