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21.
22.
The addition of 4.0 equiv of Na(silox) to Na[W(2)Cl(7)(THF)(5)] afforded (silox)(2)ClW&tbd1;WCl(silox)(2) (1, 65%). Treatment of 1 with 2.0 equiv of MeMgBr in Et(2)O provided (silox)(2)MeW&tbd1;WMe(silox)(2) (2, 81%). In the presence of 1 atm of H(2), reduction of 1 with 2.0 equiv of Na/Hg in DME provided (silox)(2)HW&tbd1;WH(silox)(2) (3, 70%), characterized by a hydride resonance at delta 19.69 (J(WH) = 325 Hz, (1)H NMR). Exposure of 2 to 1 atm of H(2) yielded 3 and CH(4) via (silox)(2)HW&tbd1;WMe(silox)(2) (4); use of D(2) led to [(silox)(2)WD](2) (3-d(2)). Exposure of 3 to ethylene ( approximately 1 atm, 25 degrees C) in hexanes generated (silox)(2)EtW&tbd1;WEt(silox)(2) (5), but solutions of 5 reverted to 3 and free C(2)H(4) upon standing. NMR spectral data are consistent with a sterically locked, gauche, C(2) symmetry for 1-5. Thermolysis of 3 at 100 degrees C (4 h) resulted in partial conversion to (silox)(2)HW&tbd1;W(OSi(t)Bu(2)CMe(2)CH(2))(silox) (6a, approximately 60%) and free H(2), while extended thermolysis with degassing (5 d, 70 degrees C) produced a second cyclometalated rotational isomer, 6b (6a:6b approximately 3:1). When left at 25 degrees C (4 h) in sealed NMR tubes, 6 and free H(2) regenerated 3. Reduction of 1 with 2.0 equiv of Na/Hg in DME also afforded 6a (25%). When 3 was exposed to approximately 3 atm of H(2), equilibrium amounts of [(silox)(2)WH(2)](2) (7) were observed by (1)H NMR spectroscopy (3 + H(2) right harpoon over left harpoon 7; 25.9-88.7 degrees C, DeltaH = -9.6(4) kcal/mol, DeltaS = -21(2) eu). Benzene solutions of 3 and 1-3 atm of D(2) revealed incorporation of deuterium into the silox ligands, presumably via intermediate 6. In sealed tubes containing [(silox)(2)WCl](2) (1) and dihydrogen (1-3 atm), (1)H NMR spectral evidence for [(silox)(2)WCl](2)(&mgr;-H)(2) (8) was obtained, suggesting that formation of 3 from 1 proceeded via reduction of 8. Alternatively, 3 may be formed from direct reduction of 1 to give [(silox)(2)W](2) (9), followed by H(2) addition. Hydride chemical shifts for 7 are temperature dependent, varying from delta 1.39 (-70 degrees C, toluene-d(8)), to delta 3.68 (90 degrees C). (29)Si{(1)H} NMR spectra revealed a similar temperature dependence of the silox (delta 12.43, -60 degrees C, to delta 13.64, 45 degrees C) resonances. These effects may arise from thermal population of a low-lying, deltadelta, paramagnetic excited state of D(2)(d)() [(silox)(2)W](2)(&mgr;-H)(4) (DeltaE approximately 2.1 kcal/mol, chi(7a) approximately 0.03), an explanation favored over thermal equilibration with an energetically similar but structurally distinct isomer (e.g., [(silox)(2)WH(2)](2)(&mgr;-H)(2), DeltaG degrees approximately 0.69 kcal/mol, chi(7b) approximately 0.25) on the basis of spectral arguments. Extended Hückel and ab initio molecular orbital calculations on model complexes [(H(3)SiO)(2)W](2)(&mgr;-H)(4) (staggered bridged 7a', EHMO), [(H(3)SiO)(2)WH(2)](2) (all-terminal 7b', EHMO), [(H(3)SiO)(2)W](2) (9', EHMO), (HO)(4)W(2)(H(4)) (staggered-bridged 7", ab initio), and (HO)(4)W(2)(H(4)) (bent-terminal 7, ab initio) generally support the explanation of a thermally accessible excited state and assign 7 a geometry intermediate between the all-terminal and staggered-bridged forms. 相似文献
23.
The PH bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to irClL2(L = PPh3, AsPh3) and IrCl(PMe2Ph)3 generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g. IrHClL2[{(MeO)2-PO}2H] and IrHCl(PMe2Ph)3[PO(OMe)2]. Addition of triphenylphosphine to a solution containing [IrCl(C8H14)2]2 and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh3)2{PO(OMe)2}, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh3)2(C5H5N){PO(OMe)2} and IrH(PPh3)2(acac){PO(OMe)2} can be obtained. The ligand arrangements in the various complexes are inferred from IR, 1H and 31P NMR data. 相似文献
24.
Smith AB Doughty VA Sfouggatakis C Bennett CS Koyanagi J Takeuchi M 《Organic letters》2002,4(5):783-786
[reaction: see text] A short, efficient, and stereocontrolled synthesis of (-)-4, an advanced ABCD subunit of the spongistatins, has been achieved. Central to the synthetic strategy is the multicomponent linchpin union of silyl dithianes with epoxides to access both the AB and CD fragments. Fragment coupling was then achieved via an efficient stereoselective aldol reaction. The linear sequence required 22 steps and proceeded in 4.0% overall yield. 相似文献
25.
26.
Treatment of HgCl(2) with 2-LiC(6)H(4)PPh(2) gives [Hg(2-C(6)H(4)PPh(2))(2)] (1), whose phosphorus atoms take up oxygen, sulfur, and borane to give the compounds [Hg[2-C(6)H(4)P(X)Ph(2)](2)] [ X = O (3), S (4), and BH(3) (5)], respectively. Compound 1 functions as a bidentate ligand of wide, variable bite angle that can span either cis or trans coordination sites in a planar complex. Representative complexes include [HgX(2) x 1] [X = Cl (6a), Br (6b)], cis-[PtX(2) x 1] [X = Cl (cis-7), Me (9), Ph (10)], and trans-[MX(2) x 1] [X = Cl, M = Pt (trans-7), Pd (8), Ni (11); X = NCS, M = Ni (13)] in which the central metal ions are in either tetrahedral (6a,b) or planar (7-11, 13) coordination. The trans disposition of 1 in complexes trans-7, 8, and 11 imposes close metal-mercury contacts [2.8339(7), 2.8797(8), and 2.756(8) A, respectively] that are suggestive of a donor-acceptor interaction, M --> Hg. Prolonged heating of 1 with [PtCl(2)(cod)] gives the binuclear cyclometalated complex [(eta(2)-2-C(6)H(4)PPh(2))Pt(mu-2-C(6)H(4)PPh(2))(2)HgCl] (14) from which the salt [(eta(2)-2-C(6)H(4)PPh(2))Pt(mu-2-C(6)H(4)PPh(2))(2)Hg]PF(6) (15) is derived by treatment with AgPF(6). In 14 and 15, the mu-C(6)H(4)PPh(2) groups adopt a head-to-tail arrangement, and the Pt-Hg separation in 14, 3.1335(5) A, is in the range expected for a weak metallophilic interaction. A similar arrangement of bridging groups is found in [Cl((n)Bu(3)P)Pd(mu-C(6)H(4)PPh(2))(2)HgCl] (16), which is formed by heating 1 with [PdCl(2)(P(n)()Bu(3))(2)]. Reaction of 1 with [Pd(dba)(2)] [dba = dibenzylideneacetone] at room temperature gives [Pd(1)(2)] (19) which, in air, forms a trigonal planar palladium(0) complex 20 containing bidentate 1 and the monodentate phosphine-phosphine oxide ligand [Hg(2-C(6)H(4)PPh(2))[2-C(6)H(4)P(O)Ph(2)]]. On heating, 19 eliminates Pd and Hg, and the C-C coupled product 2-Ph(2)PC(6)H(4)C(6)H(4)PPh(2)-2 (18) is formed by reductive elimination. In contrast, 1 reacts with platinum(0) complexes to give a bis(aryl)platinum(II) species formulated as [Pt(eta(1)-C-2-C(6)H(4)PPh(2))(eta(2)-2-C(6)H(4)PPh(2))(eta(1)-P-1)]. Crystal data are as follows. Compound 3: monoclinic, P2(1)/n, with a = 11.331(3) A, b = 9.381(2) A, c = 14.516 A, beta = 98.30(2) degrees, and Z = 2. Compound 6b x 2CH(2)Cl(2): triclinic, P macro 1, with a = 12.720(3) A, b = 13.154(3) A, c = 12.724(2) A, alpha = 92.01(2) degrees, beta = 109.19(2) degrees, gamma = 90.82(2) degrees, and Z = 2. Compound trans-7 x 2CH(2)Cl(2): orthorhombic, Pbca, with a = 19.805(3) A, b = 8.532(4) A, c = 23.076(2) A, and Z = 4. Compound 11 x 2CH(2)Cl(2): orthorhombic, Pbca, with a = 19.455(3) A, b = 8.496(5) A, c = 22.858(3) A, and Z = 4. Compound 14: monoclinic, P2(1)/c, with a = 13.150(3) A, b = 12.912(6) A, c = 26.724(2) A, beta = 94.09(1) degrees, and Z = 4. Compound 20 x C(6)H(5)CH(3).0.5CH(2)Cl(2): triclinic, P macro 1, with a = 13.199(1) A, b = 15.273(2) A, c = 17.850(1) A, alpha = 93.830(7), beta = 93.664(6), gamma = 104.378(7) degrees, and Z = 2. 相似文献
27.
Retbøll M Edwards AJ Rae AD Willis AC Bennett MA Wenger E 《Journal of the American Chemical Society》2002,124(28):8348-8360
A series of nickel(II) and palladium(II) aryl complexes substituted in the ortho position of the aromatic ring by a (pinacolato)boronic ester group, [MBr[o-C(6)H(4)B(pin)]L(2)] (M = Ni, L(2) = 2PPh(3) (2a), 2PCy(3) (2b), 2PEt(3) (2c), dcpe (2d), dppe (2e), and dppb (2f); M = Pd, L(2) = 2PPh(3) (3a), 2PCy(3) (3b), and dcpe (3d)), has been prepared. Many of these complexes react readily with KO(t)Bu to form the corresponding benzyne complexes [M(eta(2)-C(6)H(4))L(2)] (M = Ni, L(2) = 2PPh(3) (4a), 2PCy(3) (4b), 2PEt(3) (4c), dcpe (4d); M = Pd, L(2) = 2PCy(3) (5b)). This reaction can be regarded as an intramolecular version of a Suzuki cross-coupling reaction, the driving force for which may be the steric interaction between the boronic ester group and the phosphine ligands present in the precursors 2 and 3. Complex 3d also reacts with KO(t)Bu, but in this case disproportionation of the initially formed eta(2)-C(6)H(4) complex (5d) leads to a 1:1 mixture of a novel dinuclear palladium(I) complex, [(dcpe)Pd(mu(2)-C(6)H(4))Pd(dcpe)] (6), and a 2,2'-biphenyldiyl complex, [Pd(2,2'-C(6)H(4)C(6)H(4))(dcpe)] (7d). Complexes 2a, 3b, 3d, 4b, 5b, 6, and 7d have been structurally characterized by X-ray diffraction; complex 5b is the first example of an isolated benzyne-palladium(0) species. 相似文献
28.
T. Bennett D. Cavers J. M. D'Auria 《Journal of Radioanalytical and Nuclear Chemistry》1973,13(1):201-212
The purpose of this study was to demonstrate the versatility of combining the use of high resolution, Ge(Li) γ-detectors with
the techniques of fast neutron activation analysis. A compilation of γ-ray spectra are presented for irradiation of 30 elements
with 14.8 MeV neutrons under standard conditions and the origin of all major photopeaks is determined. 相似文献
29.
The response of a monoaza-15-crown-5 with an optically active aminobenzoxazinone moiety to divalent cations was investigated. The crown ether was found to undergo a strong emission shift to the blue when complexed with specific divalent metals that have ionic diameters between 1.9-2.4 A. Consequently the photoactive macrocycle is responsive to Mg(2+), Ca(2+), Ba(2+), Sr(2+), Cd(2+), and particularly responsive to Hg(2+)and Pb(2+). Macrocycle emission spectra are shown to be a function of cation concentration. Alkaline metal cations and smaller transition metals ions such as Ni(2+), Co(2+)and Zn(2+)do not cause significant changes in the macrocycle emission spectra. Emission, absorption, and complex stability constants are determined. Mechanisms of cation selectivity and spectral emission shifts are discussed. Challenges involving immobilization of the macrocycle while preserving its spectral response to cations are explored. 相似文献
30.