Synthesis and structure of the new binuclear complex η5-C5H5(CO)2Fe-η1-C5H4(CO)2Fe-CH3

Conclusions The new binuclear complex ⁵-C₅H₅(CO)₂Fe-¹-C₅H₄(CO)₂Fe-CH₃ was synthesized. Its structure was established by x-ray crystallographic analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 437–440, February, 1986.     

Structural characterization of the anionic halfsandwich complex [Li(TMEDA)2][Mo(η5-C5H5)(CO)3] and its reactivity towards stannanes and distannanes

The crystal structure of the molybdenum half sandwich alkali salt [Li(TMEDA)₂][Mo(η⁵-C₅H₅)(CO)₃] shows the occurrence of a separated ion pair in the solid state. Furthermore, the crystal structures of the long known organotin complexes [Mo(η⁵-C₅H₅)(SnMe₃)(CO)₃], [{Mo(η⁵-C₅H₅)(CO)₃}₂SnMe₂] and [Mo(η⁵-C₅H₅)(SnMeCl₂)(CO)₃] have been recorded. The chlorination of [Mo(η⁵-C₅H₅)(SnMe₃)(CO)₃] with SnCl₄ is presented as an improved synthetic access to [Mo(η⁵-C₅H₅)(SnMeCl₂)(CO)₃]. Finally, the reaction of Li[Mo(η⁵-C₅H₅)(CO)₃] with ^tBu₂(Cl)Sn–Sn(Cl)^tBu₂ leads to the novel molybdenum distannane complex [Mo(η⁵-C₅H₅){Sn^tBu₂-Sn(Cl)^tBu₂}(CO)₃], which is fully characterized by NMR, elemental and X-ray analysis.     

Synthesis of a transition metal-dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5)

The reaction of Na[η⁵-C₅H₅Fe(CO)₂] with large excess of SO₂ in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η⁵-C₅H₅)(CO)₂FeS(O)₂S(O)₂Fe(CO)₂(η⁵-C₅H₅).     

Generation and reactivity of the dehydrotropylium-Co2(CO)6 ion

Dehydrotropylium-Co(2)(CO)(6) ion (2) has been generated by the Lewis acid mediated ionization of alcohol (3); it is attacked by relatively strong nucleophiles (N>1), but undergoes a radical homocoupling in the presence of weak nucleophiles (N<1).     

硅烷基五羰基锰(CO)5MnSiR3的光化学合成

对甲基苄基五羰基锰[(CO)5Mn-p-CH2C6H4CH3,4a]或对甲氧基五羰基锰[(CO)5Mn-p-CH2C6H40CH3,4b]与1～2当量R3SiH的C6H6或C6D6溶液在5℃光解,经色谱纯化后得到中等或高收率硅烷基五羰基锰(CO)5MnSiR3:SiR3=SiMe2Ph(1b),SiMePh2(It),SiPh3(1d),SiHPh2(1e),SiEt3(1f),SiMe2-t-Bu(1g)和SiMe2Et(1h).光化学反应后,对二甲苯和对甲基苯甲醚副产物分别定量生成,并伴随少量Mn2(C0)10(<1%～6%).色谱柱的尺寸和温度(室温至--65℃)的选择视初始浓度的分解,色谱柱展开期间l的稳定性(过载),以及l与Mn2(CO)10的分离难易而定.去除Mn2(CO)10后的硅烷基五羰基锰1b～1g为浅黄色油状物或无色晶体(只有1h无法分离得到纯净物).尽管这些化合物对空气敏感对热却相对稳定.     

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.     

Synthesis and Crystal Structure of (CO)5ReSnMe2Re(CO)5

１ＩＮＴＲＯＤＵＣＴＩＯＮＨｏｍｏ ｄｉｎｕｃｌｅａｒｍｅｔａｌｃａｒｂｏｎｙｌｃｌｕｓｔｅｒｓｈａｖｅｂｅｎｓｔｕｄｉｅｄｗｉｄｅｌｙｆｏｒｔｈｅｉｒｎｏｖｅｌｓｔｒｕｃｔｕｒｅｓａｎｄｕｓｅｓｉｎｏｒｇａｎｉｃｓｙｎｔｈｅｓｉｓ〔１〕．Ｅｘａｍｐ...     

Syntheses of the linkage isomers (H2O)5CrNCCo(CN)5 and (H2O)5CrCNCo(CN)5

The slow reaction of Cr(H₂O)₆³⁺ with Co(CN)₆³⁻ produces (H₂O)CrNCCo(CN)₅. The rapid reaction of Co(CN)₅N₃³⁻ with nitrious acid in the presence of Cr)OH₂)₅CN²⁺ produces (H₂O)₅CrCNCo(CN)₅. The two binuclear complexes were separated and purified by cation and anion exchange procedures. The orientation of the bridging cyanide in the isomeric complexes was determined by a spectroscopic technique. For (H₂O)₅CrNCCo(CN)₅ the ⁴A_2g → ⁴T_2g and ⁴A_2g → ⁴T_1g of the chromium moiety are at 560 and 401 nm, respectively, and the ¹A_1g → ¹T_1g of the cobalt moiety is at 310 nm. For (H₂O)₅CrCNCo(CN)₅ the ⁴A_2g → ⁴T_2g band is at 552 nm, but the ⁴A_2g → ⁴T_1g absorption of the chromium is obscured by the ¹A_1g → ¹T_1g transition of the cobalt at 347 nm. The base hydrolysis of (H₂O)₅CNCCo(CN)₅ produces Co(CN)₆³⁻ and “chromite” quantitatively. The vase hydrolysis of (H₂O)₅CrCNCo(CN)₅ produces chromite and an unidentified cobalt(III) species that absorbs at 345–347 nm.     

Fluxional behavior of (CO)4Fe(u-AsMe2)Mo(CO)2(C5H5)

The ¹H and ¹³C NMR spectra of the heterobimetallic compound (CO)₄Fe(μ-AsMe₂)Mo(CO)₂(C₅H₅) reveal three different fluxional processes.     

Intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)2]2C6H2Sn(X)W(CO)5 (X = Cl, F, PPh2, PPh2[W(CO)5]). Syntheses and reactivity

The synthesis of the intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)Sn(X)W(CO)(5) (1, X = Cl; 2, X = F; 3, X = PPh(2)) and of 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)Sn[W(CO)(5)]PPh(2)[W(CO)(5)], 4, are reported. UV-irradiation of compound 4 in tetrahydrofurane serendipitously gave the bis(organostannylene) tungsten tetracarbonyl complex cyclo-O(2)W[OSn(R)](2)W(CO)(4) (R = 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)), 5, that contains an unprecedented W(0)-Sn-O-W(vi) bond sequence. The compounds 1-5 were characterized by means of single crystal X-ray diffraction analysis, (1)H, (13)C, (19)F, (31)P, (119)Sn NMR, and IR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and elemental analysis. Compound 4 features a hindered rotation about the Sn-P bond.     

Dihydrogen complexes of electrophilic metal centers: observation of Cr(CO)5(H2), W(CO)5(H2) and [Re(CO)5(H2)]+

Photolysis of dichloromethane solutions of M(CO)6 (M = Cr, W) at low temperature in the presence of hydrogen gas affords W(CO)5(H2) (1) and Cr(CO)5(H2) (2). Complexes 1 and 2 are characterized as dihydrogen complexes based on short T1 values for the hydride resonances and a large HD coupling of 35.3 Hz (W) and 35.8 Hz (Cr) in the HD derivatives. A cationic analogue, [Re(CO)5(H2)]+ (3), was prepared by reaction of Re(CO)5Cl with [Et3Si][B(C6F5)4] in fluorobenzene under hydrogen. Complex 3-d1 exhibits JHD = 33.9 Hz. Complex 3 is strongly acidic, with complete deprotonation by diethyl ether; complexes 1 and 2 are moderately acidic. Deprotonation of 1 is complete in the presence of one equivalent of triethylamine.     

Syntheses and Characterizations of （η~5－C_5H_5）MoFeCo（CO）_8（μ_3－S） and （η~5－C_5H_5）_2Mo_2Fe（CO）_7（μ_3－S）：X－ray Crystal Structure of （η~5－C_5H_5）MoFeCo（CO）_8（μ_3－S）

ＳｙｎｔｈｅｓｅｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｓｏｆ（η~５－Ｃ_５Ｈ_５）ＭｏＦｅＣｏ（ＣＯ）_８（μ_３－Ｓ）ａｎｄ（η~５－Ｃ_５Ｈ_５）_２Ｍｏ_２Ｆｅ（ＣＯ）_７（μ_３－Ｓ）：Ｘ－ｒａｙＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ（η~５－Ｃ_５Ｈ_...     

Unprecedented reactivity of the bridged borylene complexes [mu-BCl((eta(5)-C(5)H(4)Me)Mn(CO)(2))(2)] toward pyridine

The reactivity of the bridged chloroborylene complex [mu-BCl((eta(5)-C(5)H(4)Me)Mn(CO)(2))(2)] (1) toward pyridine was investigated under various conditions. In the presence of protic reagents such as H[Co(CO)(4)] or H[BF(4)], the formation of the aminoborylene complex [1-(mu-B)-4-H-(NC(5)H(5))((C(5)H(4)Me)Mn(CO)(2))(2)] (2) was observed. Compound 2 represents the product of an unprecedented formal 1,4-hydroboration of pyridine. Corresponding reactions of 1 with pyridine and Tl[PF(6)] afforded 2 in similar yields, thus providing evidence that the abstraction of the boron bound chloride initiates the observed reaction. Complex 2 was fully characterized in solution and in the crystal.     

2(5H)-Furanone and 5-Hydroxy-2(5H)-furanone: Reactions and Syntheses Based on Them

Russian Journal of General Chemistry - This review summarizes the data on 2(5H)-furanone, 5-hydroxy-2(5H)-furanone, and some substituted hydrofuranones with respect to their poorly studied or...     

Studies of Fe2(CO)9 Formation in the Thermolysis of Fe(CO)5 Using Ab Initio Calculations of Fe(CO)5 and Fe(CO)4

Ab initio calculations using the GAMESS program package in the atomic basis TZV (Fe: (14s, 11p, 6d)/[10s, 8p, 3d]; C, O: (11s, 6p)/[5s, 3p]) were performed with account taken of the correlation with the second-order Möller–Plesset (MP2) perturbation theory to predict a new conformer Fe(CO)₄ (with D _4h symmetry). This conformer has a square planar configuration in the ground singlet electronic state and is a mild electrophile produced by dissociation of Fe(CO)₅ along the axial Fe–C bond. The process of nucleation of iron nanoparticles Fe(CO)₅ + Fe(CO)₄ Fe₂(CO)₉ is supposed to occur in two stages. The first stage is an orbital-controlled reaction which should be monitored as an increase in medium polarity and temperature. It should proceed with participation of only one of the stable conformers of the nucleophile Fe(CO)₅, namely, a mild conformer with square-pyramidal structure (C _4v ) rather than a hard but energetically more advantageous conformer with trigonal–bipyramidal structure (D _3h ). The structure of a prereaction complex was discussed.     

双二苯基膦基吡啶钯氯化物的合成和分子结构

二苯基膦基吡啶(Ph~2PPy)同氯化钯配位反应得到配合物(PH~2PPy)~2PdCl~2.0.5CH~2Cl~2, 配合物经X衍射测定了晶体及分子结构, 该晶体属正交晶系Pcab, a=0.8050(1)nm, b=2.0152(4)nm, c=2.3067(9)nm, Z=4。晶体结构经全矩阵最小二乘修正, 得R=0.059。