- NMR study of mono- and dilithium derivatives of alkyl and arylstannanes
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Element-centered mono- and dianions of alkyl- and arylstannanes were studied by NMR spectroscopy. The 13C and 119Sn NMR chemical shifts for the dianions R2SnLi2 (R = Ph, Et) were measured for the first time.
- Chugunov,Troitskii,Nosov,Egorov,Nefedov
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- METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0044; 0052
(2016/10/31)
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- Attachment of chelating ligand pockets to tinorganyl moieties
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Several approaches have been undertaken to realize the synthesis of a new tinorganyl compound with a 2,2′,6′,2″-terpyridine moiety. A synthesis pathway consisting of five steps with an overall yield of 51 was successful in producing Ph3Sn(CH2)3OPhttpy [HOttpy = 2,6-bis(2′-pyridyl)-4′-(p-hydroxyphenyl)pyridine], and insight has been gained into (partial) halogenation reactions with this unprecedented tinorganyl compound. Halogenation with hydroiodic acid produced a new dinuclear complex cation that resulted from head-to-tail coordination of two monocations. Furthermore, synthesis and yields of already known intermediates have been optimized. The products were analyzed and identified by 119Sn NMR, 1H NMR, and 13C NMR spectroscopy and ESI mass spectrometry, as well as by means of single-crystal X-ray diffraction. A new compound Ph3SnR, comprising a 2,2′,6′,2″-terpyridine-functionalized ligand R, has been synthesized in a five-step procedure. On attempting to halogenate this compound, a partially iodinated derivative was obtained that forms a head-to-tail connected dimer in the salt [(PhISn(CH2)3OPhttpy)2](I3)2 with the terpyridine units acting as chelating ligands.
- Barth, Beatrix E. K.,Harms, Klaus,Dehnen, Stefanie
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p. 2406 - 2411
(2015/04/27)
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- Synthesis and structure of the dithienostannole anion
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Novel dithienostannoles were synthesized by the reactions of the corresponding dilithiobithiophenes with dichlorodiphenylstannane. A unique byproduct, 10-membered ring compound was also obtained. Reduction of type A dithienostannole with lithium afforded 2,2′-dilithio-3,3′-bithiophene, while reduction of type B dithienostannole with lithium afforded the corresponding dithienostannole anion. The structure and aromaticity of the dithienostannole anion are also discussed.
- Saito, Masaichi,Shiratake, Munenori,Tajima, Tomoyuki,Guo, Jing Dong,Nagase, Shigeru
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p. 4056 - 4061
(2010/03/04)
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- Syntheses and structures of 3-stannylcholest-5-ene species
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The compounds, 3α- and 3β-triphenylstannylcholest-5-ene, 1 and 2 respectively, have been prepared stereospecifically in reactions of Ph3SnLi with cholesteryl methane- or toluene-p-sulfonates, and of Ph3SnCl with the Grignard reagent from cholesteryl chloride, respectively. Complete 1H and 13C NMR spectral assignments for 1 have been obtained using HMBC and HMQC techniques: these have been used to aid the 13C NMR spectral assignments for 2 and 3α- and 3β-(InPh3-nSn)cholest-5-enes (n = 1-2) (9-12). Crystal structure determinations of 3α-(IPh2Sn)cholest-5-ene 9 and 3α-(I2PhSn)cholest-5-ene 10 indicate distorted tetrahedral geometries about the tin centres in both compounds. The Sn-I bond lengths are 2.731(5) A in 9 and between 2.6979(12) and 2.7173(12) A in 10. Despite the similarity in the values (ca. 60°) of the dihedral angles, Sn-C(3)-C(2)-C(1) [C(1) aliphatic carbon] and Sn-C(3)-C(4)-C(5) [C(5) olefinic carbon], the values of 3J[119Sn-13C(1)] are about twice the 3J[119Sn-13C(5)] values in each of 1, 9 and 10; in contrast, 3J[119Sn-13C(1)] and 3J[119Sn-13C(5)] values are essentially the same in each of 2, 11 and 12 [Sn-C(3)-C(2)-C(1) and Sn-C(3)-C(4)-C(5) ca. 180°].
- Buchanan, Heather J.,Cox, Philip J.,Doidge-Harrison, Solange M. S. V.,Howie, R. Alan,Jaspars, Marcel,Wardell, James L.
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p. 3657 - 3664
(2007/10/03)
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- UEBER GEMISCHTE BINDUNGEN IN DER IV. HAUPTGRUPPE. III. OCTAPHENYLPROPAN-ANALOGA Ph3SnSiPh2SnPh3 UND Ph3SnGePh2SnPh3, KORRELATION ZWISCHEN GEMINALEN NMR-KOPPLUNGEN 2J(Sn-M-Sn) UND NICHT-BINDENDEN Sn...Sn-ABSTAENDEN
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Reaction of Ph3SnLi with Ph2SiCl2 or Ph2GeCl2 at -78 deg C in THF yields (Ph3Sn)2SiPh2 (1) and (Ph3Sn)2GePh2 (2).The crystal structure of 1 (R=0.075) exhibits Sn-Si distances of 257.2(4) and 257.9(5) pm, an Sn-Si-Sn angle of 118.5(2) deg, and a central C3Sn-SiC2-SnC3 molecular skeleton with symmetry close to C2.The geminal NMR coupling 2J(119 Sn...119 Sn) in 1, and in a tri-, tetra- and pentastannane series shows a linear correlation to their respective non-bonded d(Sn...Sn) distances (I(t-Bu2Sn)4I: 20 Hz/496 pm; 1: 724 Hz/443 pm).
- Adams, Stefan,Draeger, Martin
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- Laser Photolysis and CIDEP Studies of the Formation of Phenyl-Substituted Group 4B Element (Silicon, Germanium, and Tin)-Centered Radicals in Direct Photoejection of the Group 4B Element-Centered Anions
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Phenyl-substituted group 4B element-centered radicals generated by the direct photoejection from the group 4B element-centered anions were observed by laser photolysis at room temperature.In order to claify the mechanism of this process, CIDEP study of the photolysis of the group 4B element-centered anions was carried out at 77 and 4.2 K.From the emissive patterns observed for the germyl and stannyl anions after the excitation by a pluse laser, the photoejection reactions were most probably considered to occur from triplet anions.
- Mochida, Kunio,Wakasa, Masanobu,Sakaguchi, Yoshio,Hayashi, Hisaharu
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p. 7942 - 7947
(2007/10/02)
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- Highly reduced organometallics. 14. Six- and seven-coordinate organotin derivatives of the tetrasodium tetracarbonylmetalates(4-) of chromium, molybdenum, and tungsten
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Treatment of Na4[M(CO)4] with 2 equiv of Ph3SnCl provides approximately 50% yields of [Et4N]2[(Ph3Sn)2M(CO)4] for M = Cr and W and very low yields for M = Mo. The reaction of L2M(CO)4, where L2 = norbornadiene, cyclooctadiene, tetramethylethylenediamine, or ethylenediamine (M = Cr, Mo, W), with 2 equiv of Ph3SnLi is a more facile and often higher yield route (60-70% for M = Cr, Mo; 35% for M = W) to the same dianions. These materials react with Ph3SnCl to provide 30-40% yields of [Et4N][(Ph3Sn)3M(CO)4], in which Cr, Mo, and W are seven-coordinate. Reactions of [Et4N]2-[(Ph3Sn)2M(CO)4] (M = Cr, Mo) with acetic acid, [Me2NCCl2]Cl, and methyl iodide in acetonitrile provide 30-40% yields of [Et4N][H(Ph3Sn)2M(CO)4], containing seven-coordinate metals, trans-Ph3Sn(CO)4M≡ CNMe2, and [Et4N][(Ph3Sn)M(CO)4(CH3CN)], respectively. The coordinated acetonitrile in the latter compounds is slowly displaced by PPh3 in acetonitrile at 25°C to give 35-50% yields of [Et4N]-[Ph3SnM(CO)4(PPh3)]. All of these new materials are characterized by elemental analyses and IR and 1H NMR spectra.
- Lin, Jiann T.,Hagen, Gary P.,Ellis, John E.
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p. 1145 - 1150
(2008/10/08)
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- Compounds of the Triphenyltin(II) Ion
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Ionic compounds R+SnPh3-, where R = Me4N, (Ph3P)2N, Na(15-crown-5) or K(18-crown-6), are prepared from alkali metal derivatives, Ph3SnM, by reactions in liquid ammonia which yield the products as yellow crystalline solids, soluble in a weakly basic solvent.N.m.r and vibrational spectra of the Ph3Sn- anion, a pyramidal species with C3υ symmetry, and the cationic complexes +, are reported and assigned.
- Bullard, Wayne R.,Taylor, Michael J.
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p. 1337 - 1340
(2007/10/02)
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