15038-48-9Relevant articles and documents
Reactions of tetracyclone molybdenum complexes with electrophilic alkynes: Cyclopentadienone-alkyne coupling and alkyne coordination
Adams, Harry,Booth, Yvonne K.,Cook, Elizabeth S.,Riley, Sarah,Morris, Michael J.
, p. 2254 - 2261 (2017)
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.
CHROMIUM, MOLYBDENUM AND TUNGSTEN CARBONYL DERIVATIVES OF AN UNUSUAL OXYGEN TRIPOD LIGAND
Klaeui, W.,Mueller, A.,Scotti, M.
, p. 45 - 52 (1983)
(Cyclopentadienyl)tris(diethylphosphito-P)cobaltate(1-), 3>-, reacts as an oxygen tripod ligand L- with (CH3CN)3M(CO)3 (M = Cr, Mo, W) in water to produce the tricarbonyl complexes -.These a
Synthetic, structural, NMR, and computational study of a geminally bis(peri-substituted) tridentate phosphine and its chalcogenides and transition-metal complexes
Ray, Matthew J.,Randall, Rebecca A. M.,Arachchige, Kasun S. Athukorala,Slawin, Alexandra M. Z.,Buehl, Michael,Lebl, Tomas,Kilian, Petr
, p. 4346 - 4359 (2013)
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.
Crystal structures of [K(2.2.2-crypt)]4[Pb9Mo(CO) 3] - Isolation of the novel isomers [(η5-Pb 9)Mo(CO)3]4- beside [η4-Pb 9Mo(CO)3]4-
Yong, Li,Hoffmann, Stephan D.,Faessler, Thomas F.
, p. 3663 - 3669 (2005)
The reaction of [Mo(CO)3(MeCN)3] with K 4Pb9 in the presence of 2.2.2-cryptand (2.2.2-crypt) has been investigated. The transition metal complex [K(2.2.2-crypt)] 4[(η5-Pb9)-Mo(CO)3] (1), which contains a Pb94- Zintl anion coordinated by Mo in an η5-fashion, is isolated for the first time and characterized by single-crystal X-ray structure analysis. The 10 metal atoms in the [(η5-Pb9)Mo(CO)3]4- anion form a bi-capped square antiprism, with the Mo(CO)3 unit occupying a waist vertex position. The IR spectra of single crystals, as well as of the crude product, show clearly that only the [(η5-Pb9)Mo(CO) 3]4- ion is formed. In contrast, the reaction of [Mo(CO)3(Mes)] with K4Pb9 under the same reaction conditions gives a mixture of compound 1 and its isomer [K(2.2.2-crypt)]4[(η4-Pb9)Mo(CO) 3] (2). Compounds 1 and 2 were isolated without additional solvent molecules. The Pb-Mo, Pb-Pb, and Mo-C bond lengths and Mo-C-O bond angles in the η4- and η5-isomers are compared and the packing of compounds 1 and 2 is discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
Synthesis and structures of dinuclear iron, molybdenum and tungsten complexes derived from (PhCHCHPh)-coupled bis(cyclopentadiene)
Li, Bin,Wang, Baiquan,Xu, Shansheng,Zhou, Xiuzhong
, p. 5309 - 5317 (2005)
Reductive coupling of phenylfulvene with amalgamated calcium metal followed by hydrolysis yields CpPhCHCHPhCp (1) in high yield. Refluxing ligand 1 and Fe(CO)5 in xylene produces (PhCHCHPh)-coupled bis(cyclopentadienyl) tetracarbonyl diiron (PhCHCHPh)[(η5-C5H 4)Fe(CO)2]2 (2) as a mixture of meso (2-meso) and racemic isomers (2-rac). The pure racemic isomers of the Mo and W analogues (3-rac and 4-rac) have been synthesized by lithiation of ligand 1 and addition of (MeCN)3M(CO)3 (M = Mo, W) followed by oxidation with 2 equiv. of ferrocenium tetrafluoroborate. All the new complexes have been fully characterized. The molecular structures of 1-meso, 2-meso, 2-rac, 3-rac, and 4-rac have been determined by X-ray diffraction analysis.
Tris[(alkylthio)methyl]silanes: Syntheses and structures of chromium, molybdenum, and tungsten complexes with a tripodal thioether ligand
Yim, Hing W.,Tran, Linh M.,Dobbin, Ebern D.,Rabinovich, Daniel,Liable-Sands, Louise M.,Incarvito, Christopher D.,Lam, Kin-Chung,Rheingold, Arnold L.
, p. 2211 - 2215 (1999)
The first member of a new family of tripodal thioether ligands, the methyltris[(alkylthio)methyl]silanes MeSi-(CH2SR)3 (R = Me), has been synthesized and characterized. Reactivity studies lead to the isolation of the complete series of group 6 metal carbonyl derivatives {η3-MeSi(CH2SMe)3}M(CO)3 (M = Cr, Mo, W), whose structures have been determined by single-crystal X-ray diffraction. The three complexes are isomorphous and display distorted octahedral structures with face-capping tridentate thioether ligands. {η3-MeSi(CH2SMe)3}Cr(CO)3 is monoclinic, P21/c, a = 8.1658(2) A?, b = 15.0563(2) A?, c = 26.5791(3) A?, β= 90.3653(6)°, V = 3267.74(8) A?3, Z = 8. {η3-MeSi(CH2SMe)3}Mo(CO)3 is monoclinic, P21/c, a = 8.34630(6) A, b = 15.2747(2) A?, c = 27.1865(4) A?, β = 90.8987(9)°, V= 3465.44(10) A?3, Z = 8. {η3-MeSi(CH2SMe)3}W(CO)3 is monoclinic, P21/c, a = 8.1582(2) A?, b = 14.9903(2) A?, c = 26.7268(4) A?, β = 90.6568(8)°, V = 3268.30(9) A?3, Z = 8.
Formation of clusters by oxidative addition of organic and inorganic disulfides. Molecular structures of (MeCN)2(CO)6Mo2(μ-SPh)2 and Mo2Fe7S8(CO)22
Eremenko, I. L.,Pasynskii, A. A.,Abdulaev, A. S.,Aliev, A. S.,Orazsakhatov, B.,et al.
, p. 297 - 308 (1989)
Reactions of the disulfides Ph2S2 and (CO)6Fe2S2 with (MeCN)3Mo(CO)3 (I) leading to the splitting of S-S bonds have been studied.Binuclear (MeCN)2(CO)6Mo2(μ-SPh)2 (II) is obtained from the reaction of I with Ph2S2.The X-ray diffraction data for II (space group P21, a 9.262(4), b 9.343(10), c 15.494(6), β 105.85(3), Z=2, R=0.037) show the Mo-Mo bond of length (2.982(1) Angstroem), to be supported by thiolate bridges (Mo-S 2.468(1) Angstroem).Interaction of I with the ferrosulfide dimer breaks the S-S and the Fe-Fe bonds to give an antiferromagnetic nonanuclear cluster Mo2Fe7S8(CO)22 (III) (μeff 2.61(298 K) - 1.92(78 K) BM).An X-ray diffraction study (space group P1, a 13.003(2), b 14.278(1), c 16.019(2) Angstroem, α=109.555(8), β 97.187(10), γ 113.006(7) deg, Z=2, R=0.045) has revealed that molecule III consists of two fragments (CO)9Fe3(S)4Mo(CO)2 (Mo-Fe 2.750(2) Angstroem, Fe-S 2.260(3) Angstroem, Mo-S 2.406(3) Angstroem) linked via the Fe atom (Mo-Fe 2.900(2) Angstroem, Fe-S 2.242(3) and 2.529(3) Angstroem), but without Fe-Fe bonds.
Carborane Stabilized 19-Electron Molybdenum Metalloradical
Jaiswal, Kuldeep,Malik, Naveen,Tumanskii, Boris,Ménard, Gabriel,Dobrovetsky, Roman
supporting information, p. 9842 - 9848 (2021/07/21)
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
Zaitsev, Kirill V.,Lam, Kevin,Tafeenko, Viktor A.,Korlyukov, Alexander A.,Poleshchuk, Oleg Kh.
, p. 4911 - 4924 (2018/12/11)
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.
Synthesis of a carbon analogue of scytonemin
Mukai, Chisato,Arima, Katsuya,Hirata, Shuichi,Yasuda, Shigeo
, p. 273 - 277 (2015/04/22)
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.
