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The push,pull effect in two series of disubstituted alkynes was studied at the DFT level [B3LYP/6-311G(d)] by application of the 13C chemical shift differences (GIAO) between the alkyne carbon atoms (ΔδCC), the charge difference between these carbons (ΔqCC), the occupation quotient (NBO) of anti-bonding π∗, and bonding π orbitals (π∗CC/πCC) and the bond length (dCC) of the CC triple bond. The linear dependence of dCC versus π∗CC/πCC quantifies changes in the push,pull effect while deviations from the latter correlation indicate and ascertain quantitatively to what extent steric hindrance restricts the strain-less conjugation of the CC triple bond π-orbitals in the disubstituted alkynes. 相似文献
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Jason M. Lynam Tracy D. Nixon Adrian C. Whitwood 《Journal of organometallic chemistry》2008,693(19):3103-3110
Reaction of cis-[RuCl2(dppm)2] (dppm = 1,2-bis(diphenylphosphino)methane) with PhCCH and NaPF6 utilising methanol as solvent results in the formation of the η3-butenynyl complex [Ru(η3-PhCCCCHPh)(dppm)2][PF6] in good yield. Similar reactions with ButCCH and PrnCCH resulted in the corresponding alkyl-substituted complexes and all three of these compounds have been characterised by NMR spectroscopy and X-ray crystallography. The mechanism of this reaction has been probed by employing labelling experiments with both PhCCD and PhC13CH allowing the identity of possible intermediates in the reaction to be determined. Furthermore, [Ru(η3-PhCCCCHPh)(dppm)2][PF6] has been shown to be an effective regio- and stereo-selective catalyst for the dimerisation of PhCCH to Z-PhCCCHCHPh in the absence of solvent. In contrast, no evidence for the formation of alkyne coupling was obtained from the reaction of cis-[RuCl2(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) with PhCCH and NaPF6. 相似文献
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David J. Armitt Jonathan C. Morris Allan H. White 《Journal of organometallic chemistry》2009,694(1):1-8561
In contrast to the usual formal [2+2]-cycloaddition reaction, (NC)2CC{CC(SiPri3)}2, containing bulky alkynyl substituents, reacts with Ru(CCPh)(PPh3)2Cp to give the unprecedented cyclobutenylidene complex Ru{C(CN)2C[CC(SiPri3)]CC(SiPri3)CPhC}(PPh3)Cp, formed by addition of one of the CC(SiPri3) groups to the Ru-CCPh moiety and subsequent electronic reorganisation. 相似文献
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Michael I. Bruce Martin Jevric Mark E. Smith Natasha N. Zaitseva 《Journal of organometallic chemistry》2006,691(3):361-370
The syntheses of several diynylgold(I) phosphine complexes, including Au(CCCCH){P(tol)3} (1), Au(CCCCSiMe3)(PR3) (R = Ph 2-Ph, tol 2-tol), Au(CCCCFc)(PPh3) (3), {(tol)3P}Au(CC)nAu{P(tol)3} [n = 2 (4), 3 (6), 4 (7)], {(Ph3P)Au}CCCC{Au[P(tol)3]} (5), [ppn][Au{CCCCAu[P(tol)3]}2] (8), [Au2(μ-I)(μ-dppm)2][Au(CCCCSiMe3)2] (9), Hg{CCCCAu(PR3)}2 (R = Ph 10-Ph, tol 10-tol) and {(triphos)Cu}CCCC{Au[P(tol)3]} (11) are described. Of these, the X-ray molecular structures of 1, 2-tol, 3, 4 and 9 have been determined. 相似文献
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Michael I. Bruce Kathy A. Kramarczuk Brian W. Skelton 《Journal of organometallic chemistry》2005,690(6):1549-1555
The Pd(0)/Cu(I)-catalysed reactions between Co3(μ3-CBr) (CO)9 and W(CCCCH)(CO)3Cp gives the C5 complex {Cp(OC)3W}CCCCC{Co3(CO)9} (2). Similarly, Co3(μ3-CBr)(μ-dppm)(CO)7 and W(CCCCH)(CO)3Cp or Ru(CCCCH)(dppe)Cp* give {Cp(OC)3W}CCCCC{Co3(μ-dppm)(CO)7} and {Cp*(dppe)Ru}CCCCC{Co3(μ-dppmn)(CO)7} (5). An attempt to prepare a C3 analogue from Ru(CCH)(PPh3)2Cp and Co3(μ3-CBr)(CO)9 gave instead the acyl derivative {Cp(Ph3P)2Ru}CCC(O)C{Co3(CO)8(PPh3)} (7). The X-ray structures of 2, 5 and 7 are reported: the C5 chains in 2 and 5 have an essentially unperturbed -CC-CC-C formulation. 相似文献
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Izabela Czelu?niak 《Journal of organometallic chemistry》2011,696(18):3023-3028
The reactions of tin tetrachloride and four terminal alkynes (PhCCH, tBuCCH, nBuCCH, HOCH2CCH), norbornene, and norbornadiene in dichloromethane or chloroform solution lead to the formation of stannylation products, which were characterized by 1H, 13C and 119Sn NMR spectroscopy. Virtually complete α-regioselectivity was obtained in reaction of all four alkynes without any effect of the relative steric bulk of the substituent R at the triple bond of alkyne RCβCαH. The reaction of norbornene and norbornadiene with SnCl4 is stereoselective, giving an exo stannylation product. 相似文献
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Michael I. Bruce Martyn Jevric Wyona Patalinghug Brian W. Skelton Natasha N. Zaitseva 《Journal of organometallic chemistry》2008,693(17):2915-2920
Addition of [I(py)2]BF4 to Ru(CCH)(dppe)Cp∗ gave the iodovinylidene [Ru(CCHI)(dppe)Cp∗]BF41, which could be deprotonated to Ru(CCI)(dppe)Cp∗ 2. The attempted preparation of Ru(CCCCI)(dppe)Cp∗, followed by derivatisation with tcne, gave the dienynyl Ru{CCC[C(CN)2]CIC(CN)2}(dppe)Cp∗ 3. The Pd(0)/Cu(I)-catalysed reaction of 3 with Ru{CCCCAu(PPh3)}(dppe)Cp∗ afforded Ru{CCCC(CN)2CC(CN)2Au(PPh3)}(dppe)Cp∗ 4 by formal replacement of I+ by [Au(PPh3)]+. XRD structures of 1-4 are reported. 相似文献
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The first luminescent rhenium(I)-gold(I) hetero organometallics, Re{phenAu(PPh3)}(CO)3Cl (3) and Re{(PPh3)AuphenAu(PPh3)}(CO)3Cl (4), have been prepared using the gold(I) complex AuCl(PPh3) (PPh3 = triphenylphosphine) and the novel rhenium(I) complexes Re(phenH)(CO)3Cl (5) (phenH = 3-ethynyl-1,10-phenanthroline) or Re(HphenH)(CO)3Cl (6) (HphenH = 3,8-bis(ethynyl)-1,10-phenanthroline). All the present rhenium(I) complexes 3-6 were revealed to possess a facial configuration (fac-isomer) with respect to the three carbonyl ligands. The main frameworks for these new gold(I) organometallics were constructed by the Au-C σ-bonding (with the η1-type coordination) between the ethynylphenanthrolines and the Au(I) phosphine unit. Re(I)-Au(I) heterometallics 3 and 4 have shown single phosphorescence from the 3MLCT excited state and this observation can be interpreted in terms of the efficient intramolecular energy transfer from the Au(I) unit to the Re(I) unit. 相似文献
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Pradeep Mathur Radhe Shyam Ji Amrendra K. Singh 《Journal of organometallic chemistry》2010,695(17):1986-141
Photolysis of a hexane solution containing ironpentacarbonyl, 1-ferrocenyl-4-phenyl-1,3-butadiyne at low temperature yields six new products: [Fe(CO)2{η2:η2-PhCCCC(Fc)C(CCPh)C(Fc)Fe(CO)3}-μ-CO] (1), [Fe2(CO)6{μ-η1:η1:η2:η2-PhCCCC(Fc)-C(O)-C(Fc)CCCPh}] (2), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCC(CC Ph)-C(O)-C(Fc)CCCPh}] (3), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCCCC(Fc)-C(O)-C(Fc)CCCPh}] (4), [Fe(CO)3{μ-η2: η2-[FcCC(CCPh)C(CCPh)C(Fc)}CO] (5) and [Fe(CO)3{μ-η2: η2-[FcCC(CCPh)C(CCPh)C(Fc)}CO] (6) formed by coupling of acetylenic moieties with CO insertion on metal carbonyl support. In presence of CO, formation of another new product 2,5-bis(ferrocenyl)-3,6-bis(tetracarbonylphenylmaleoyliron)quinone (7) was observed which on further reaction with ferrocenylacetyene gave the quinone, 2,5-bis(ferrocenyl)-3,6-bis(ethynylphenyl)quinone (8). Structures of 1-5 and 8 were established crystallographically. 相似文献