Unexpected formation of Fe2(CO)6(S3CH2) upon the reaction of styrene with Fe3(CO)12 and sulfur

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, p. 1705, July, 1989.     

Reaction of trialkyl-(3-aminopropyl)silanes with formaldehyde and elemental sulfur

Conclusions N-(3-Trialkylsilylpropyl)formamides (II) and N,N-bis(3-trialkylsilylpropyl)thioureas (III), together with a small amount of the trialkyl-(3-isothiocyanatopropyl)silane, are formed when trialkyl-(3-aminopropyl)silanes are reacted with formaldehyde and sulfur in aqueous-ethanol medium. 1,3,5-Tris(trialkylsilylpropyl)hexahydrotriazines are the intermediate products in these reactions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 666–668, March, 1977.     

Reaction of indolizines with elemental sulfur

The fusion of 3,8-diphenyl-, 1,2-diphenyl-, and 6-methyl-2,7-diphenyl-indolizines with sulfur results in the formation of bis(indolizin-3-yl) disulfides with the respective substituents. Bis(2,8-diphenylindolizin-3-yl) disulfide is reduced to the original indolizine, and its treatment with nitric acid gives 2,8-diphenyl-1, 3-dinitroindolizine. Bis(dibenzo[b,g]indolizin-11-yl) disulfide is obtained from dibenzo[b,g]indolizine. The formation of the disulfides is apparently a general region of indolizines without substituents at C₃ or C₁ of the pyrrole ring. The structures of the disulfides obtained have been confirmed by data from x-ray diffraction analysis and NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1371–1375, October, 1984.     

Reaction of gem-trichloroalkanes with unsaturated compounds in presence of Fe(CO)5 and a cocatalyst

Conclusions The following reactions were effected in the presence of the coordination initiators Fe(CO)₅ + i-C₃H₇OH (or Hexametapol): a) Telomerization of vinyl chloride with 1,1,1-trichloropropane and 1,1,1,3,3-pentachloropropane. Telomers that contain 1–3 monomeric units in the molecule were isolated, b) The addition of 1,1,1,3-tetrachloropropane and 1,1,1-trichloroethane to isobutylene; the adducts were obtained in good yields, c) The reaction of allyl chloride with 1,1,1,3-tetrachloropropane, which leads to the formation of the adduct and by-products as the result of the partial fragmentation of the ClCH₂CH₂CCl₂CH₂CHCH₂Cl radicals with the cleavage of chlorine atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 174–177, January, 1977.     

Reaction of 1,2-bis(cyclopentadienyl)tetramethyl digermane with Ru3(CO)12

We have recently reported a novel rearrangement reaction involving an intramolecular metathesis between M-M and Fe-Fe bonds in the dinuclear iron complexes (Me₂MMMe₂)[η⁵-C₅R₄)Fe(CO)]₂(μ-CO)₂ (M=Si, Ge; R=H, Me):^[1-5].In order to extend the applied range of the rearrangement reaction we tried to synthesize the digermyl briged diruthenium analogues. The results showed a great difference between them.     

Unexpected Reaction of Fe3(CO)12 with Dialkyldithiophosphate: The Case of P–S Bond Activation

The reaction of Fe₃(CO)₁₂ with O,O′‐dialkyldithiophosphate diethylamine salts (RO)₂P{S}SH · Et₂NH (R = CH₃, CH₂CH₃) resulted in the formation of trinuclear cluster complex {μ‐SP(OR)₂Fe[S₂P(OR)₂)]S‐μ]}Fe₂(CO)₆ [R = CH₃ ( 1 ), CH₂CH₃ ( 2 )]. The two complexes were characterized by elemental analysis, FT‐IR, NMR (¹H, ³¹P and ¹³C) spectroscopy, as well as by X‐ray diffraction analyses. Crystal structures reveal that one P–S bond is cleaved during the reaction, yielding the [2Fe2S] unit together with FePS₃(CO)₂. The other dialkyldithiophosphate coordinated with iron by S, S chelating model. The trinuclear cluster was observed with the P‐Fe and S–Fe bond formed by the P‐S activation. In addition, the electrochemical properties for complex 2 as an illustration was also studied by cyclic voltammetry in MeCN.     

Unraveling the photochemistry of Fe(CO)5 in solution: observation of Fe(CO)3 and the conversion between 3Fe(CO)4 and 1Fe(CO)4(Solvent)

The photochemistry of Fe(CO)5 (5) has been studied in heptane, supercritical (sc) Ar, scXe, and scCH4 using time-resolved infrared spectroscopy (TRIR). 3Fe(CO)4 ((3)4) and Fe(CO)3(solvent) (3) are formed as primary photoproducts within the first few picoseconds. Complex 3 is formed via a single-photon process. In heptane, scCH4, and scXe, (3)4 decays to form (1)4 x L (L = heptane, CH4, or Xe) as well as reacting with 5 to form Fe2(CO)9. In heptane, 3 reacts with CO to form (1)4 x L. The conversion of (3)4 to (1)4 x L has been monitored directly for the first time (L = heptane, kobs = 7.8(+/- 0.3) x 10(7) s(-1); scCH4, 5(+/- 1) x 10(6) s(-1); scXe, 2.1(+/- 0.1) x 10(7) s(-1)). In scAr, (3)4 and 3 react with CO to form 5 and (3)4, respectively. We have determined the rate constant (kCO = 1.2 x 10(7) dm3 mol(-1) s(-1)) for the reaction of (3)4 with CO in scAr, and this is very similar to the value obtained previously in the gas phase. Doping the scAr with either Xe or CH4 resulted in (3)4 reacting with Xe or CH4 to form (1)4 x Xe or (1)4 x CH4. The relative yield, [(3)4]:[3] decreases in the order heptane > scXe > scCH4 > scAr, and pressure-dependent measurements in scAr and scCH4 indicate an influence of the solvent density on this ratio.     

Reaction of 1,1-dichloro-1-nitrosoalkanes with the acid chloride of S-ethylmethylphosphorous acid in the presence of sulfur dioxide

1,1-Dichloro-1-nitrosoalkanes react exothermally with the acid chloride of S-ethylmethylphosphorous acid to give O-alkylchloroformiminophosphoranes, which are converted in the presence of SO₂ to O-alkylchloroformimino-S-ethylmethylphosphonates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 464–465, February, 1990.     

Reaction of styrene with sulfur and triiron dodecacarbonyl and the molecular structure of the complex Fe2(CO)6(SCH2S)

Reaction of excess styrene with Fe₃(CO)₁₂ and sulfur (60°C, 15 h, Ar, S/Fe₃(CO)₁₂ 0.6 g-atom/mole) gave Fe₂(CO)₆S₂, Fe₃(CO)₉S₂, Fe₂(CO)₆(S₂CO), Fe₂(CO)₆S₂(PhCHCH₂), PhCHCH₂S₄, and a novel binuclear complex Fe₂(CO)₆(S₂CH₂S), whose structure was analyzed by x-ray crystallography. The crystals are monoclinic, a=7.764(3), b=13.205(4), c=6.628(6) Å, =98.97(3)°. V=671.2(7) ų, Z=2, space group P2₁/m. The bond lengths are Fe-Fe 2.520(2), Fe-S 2.236(2), S-S 2.078(4), C-S 1.825(12), Fe-CO 1.784(8), and CO 1.148(9) Å.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 930–934, April, 1991.     

Fe3(CO)12与P(NEt2)2Cl的反应--两核和三核铁羰基簇合衍生物的合成和晶体结构

Fe_3(CO)_(12)与配位基前体P(NEt_2)_2Cl反应,给出4个新的两核和三核铁羰基簇合衍生物:Fe_2(CO)_6(μ-Cl)[μ-P(NEt_2)_2](Ⅰ),Fe_2(CO)_6[μ-P(NEt_2)_2]_2(Ⅱ),Fe_3(CO)_9(μ-CO)(μ_3-PNEt_2)(Ⅲ)和Fe_3(CO)_9(μ_3-PNEt_2)[P(NEt_2)_3](Ⅳ)。在反应期间,配前体分子中的P-Cl和P-N键劈开,形成的分子片Cl、PNEt_2、P(NEt_2)_2和P(NEt_2)_3作为配体与铁羰合物重新组建成上述簇合物。利用X射线衍射法测定了它们的晶体结构。Ⅰ属三斜晶系,P1空间群,晶胞参数a=0.8745(6)nm,b=0.9601(7)nm,c=1.3996(10)nm,α=74.131(11)°,β=79.480(12)°,γ=69.727(12)°,V=1.0553(13)nm~3,D_c=1.543g·cm~(-3),Z=2,R=0.0443,wR=0.0831。Ⅱ属正交晶系,Pbcn空间群,晶胞参数a=1.0153(3)nm,b=1.7543(5)nm,c=1.6860(5)nm,V=3.0031(15)nm~3,D_c=1.394g·cm~(-3),Z=4,R=0.0519,wR=0.1035。Ⅲ属单斜晶系,P2_1/c空间群,晶胞参数a=1.0280(5)nm,b=1.2113(5)nm,c=1.9192(7)nm,β=93.560(7)°,V=2.1366(16)nm~3,D_c=1.712g·cm~(-3),Z=4。Ⅳ属单斜晶系,Cc空间群,晶胞参数a=1.5875(7)nm,b=1.0359(5)nm,C=2.1919(9)nm,β=101.266(8)°,V=3.535(3)nm~3,Dc=1.443g·cm~(-3),Z=4。Ⅰ和Ⅱ为两核铁簇,其簇骨架Fe_2PCl和Fe_2P_2呈蝶状。Ⅲ和Ⅳ     

On the molecular structure of [Fe3(CO)12] in the solid state

The determination of precise, low-temperature crystal structures of [Fe₃(CO)₁₂] has shown that, on decreasing the temperature, the bridging ligands become progressively more symmetric, the bridged FeFe bond shortens and the atomic displacement parameters show a congruent behaviour with temperature.     

Reaction of 3-(N-phenylamino)-1-p-tolylprop-2-en-1-one with Ru3(CO)12

Russian Chemical Bulletin -     

Activation of a carbon—nitrogen triple bond in the presence of Ru3(CO)12 and H4Ru4(CO)12

The reaction of PhCN with Ru₃ (CO)₁₂ in the presence of acetic acid gives H₄Ru₄(CO)₁₂, (I), (μ-H)Ru₃(CO)₁₀(μ-NCHPh) (II) and (μ-H)Ru₃(CO)₁₀(μ-NH-CH₂Ph) (III) as the main products. Reaction under 110 atm of H₂ gives more III and also gives benzylamine. Replacement of acetic acid by H₂ at atmospheric pressure gives only II. When H₄Ru₄CO)₁₂ reacts with PhCN alone or in the presence of NaOH, II is formed as the only product.The structures of II and III have been fully elucidated by X-ray methods. The nitrogen atom of the NCHPh ligand in II and that of the NHCH₂Ph ligand in III, interact with the isosceles-triangular metal cluster, symmetrically bridging the shortest Ru(1)-Ru(2) edge. A hydride ligand in both II and III bridges the same Ru(1)-Ru(2) edge of the cluster. Under mild conditions acetic acid is an essential requirement for the activation of Ru₃(CO)₁₂ for reaction with PhCN to give III, which cannot be obtained under these conditions from II.