38117-54-3Relevant academic research and scientific papers
Synthesis of heteronuclear di- and tri-metal μ-carbyne compounds from the thiocarbyne (CO)2WCSMe
Doyle, Ruth Ann,Angelici, Robert J.,Gordon F.,Stone, A.
, p. 81 - 90 (1989)
The compound (CO)2WC-SMe (1) reacts with two equivalents of (In)Rh(CO)2, where In = η5-indenyl, C9H7, in refluxing THF to give the brown-black crystalline μ3-carbyne > (2) containing a Rh2W triang
Synthesis and structure of [(NMe2)3TiFe(CO)2(Cp)]: A stable iron-titanium bond
Sartain, William J.,Selegue, John P.
, p. 1812 - 1815 (1987)
[Ti(NMe2)4] reacts with [FeH(CO)2(Cp)] to form [(NMe2)3 TiFe(CO)2(Cp)] (1), by the elimination of 1 equiv of HNMe2. This compound was spectroscopically characterized, and its structure was determined by single-crystal X-ray diffraction (R = 4.0%, Rw = 4.4%). There is a direct, unsupported bond between iron and titanium in 1, with bond lengths of 2.567 (1) and 2.569 (1) ? in two independent molecules. The relative orientation of the ligands on iron and titanium suggests that there may be a π-component of the metal-metal bond. Amide methyl groups distal to iron show unusually obtuse Ti-N-C angles of about 130°. Analogous complexes with alkoxide ligands on titanium are more labile than 1.
Synthesis and characterization of a polycarbon organometallic cluster, [PPN]2[Fe6(CO)18C4]
Norton,Shriver
, p. 5118 - 5120 (2000)
The polycarbon metal cluster [Fe6(CO)18C4]2- is formed by the reaction of CF3SO3SO2CF3 with [Fe3(CO)9(CCO)]2-. Apparently, the SO2CF3 moiety abstracts an oxygen from the ketenylidene (CCO) ligand and C - C coupling occurs to form the C4 ligand. A single-crystal X-ray structure determination reveals that the pattern of C-C bond lengths of the C4 ligand in [Fe6(CO)18C4]2- mimic those in free butadiene.
One-electron reduction of molybdenum η2(4e)-alkyne complexes as a pathway to the η2(3e) vinyl ligand
Baines, Sarah,Cowley, Michael J.,Chafen, Andrew R.,Lynam, Jason M.,Spinks, Deborah C.,Whitwood, Adrian C.
, p. 1093 - 1095 (2007)
Reaction of the molybdenum alkyne complex [Mo-(P{OMe}3) 2(η2{4e}-PhC2Ph)(η5-C 5H5)][BF4] with K[Fe(CO)2- (η5-C5H5)] results in the formation of the η2(3e)-vinyl complex [Mo(P{OMe}3)2(η 2{3e}=CPh-CHPh)(η5-C5H5)] and [Fe-(CO)2(η5-C5H5)] 2. A study of the reaction by EPR spectroscopy implies that the reaction proceeds via [Mo(P{OMe}3)2(η2{4e}- PhC2Ph)(η5-C5H5)], which is then thought to undergo a hydrogen-abstraction reaction to give the observed product. The same radical was observed in the reaction of [Mo(P{OMe} 3)2-(η2{4e}-PhC2Ph) (η5-C5H5)][BF4] with LiBEt 3H, implying the presence of an alternative mechanistic pathway to the direct addition of hydride to the molybdenum alkyne complex.
Preparation and Chiroptical Properties of Optically Active Vinyl Ether-Iron and Olefin-Iron Complexes. A CD Quadrant Rule Correlating Absolute Configurations.
Begum, M. Kohinoor,Chu, Kai-Hsuan,Coolbaugh, Thomas S.,Rosenblum, Myron,Zhu, Xiao-Ya
, p. 5252 - 5259 (1989)
Exchange etherification of dicarbonylcyclopentadienyl(η2-ethyl vinyl ether)iron tetrafluoroborate (4) with optically active primary and secondary alcohols yields a mixture of diastereomeric cations.These isomers are in rapid equilibrium at room
MEHRFACHBINDUNGEN ZWISCHEN HAURTGRUPPENELEMENTEN UND UEBERGANGSMETALLEN. XXXII. INSERTIONS- UND METATHESEREAKTIONEN VON METALLORGANISCHEN EISEN-SELEN-KOMPLEXEN
Herrmann, Wolfgang A.,Rohrmann, Juergen,Herdtweck, Eberhardt,Hecht, Christian,Ziegler, Manfred L.,Serhadli, Orhan
, p. 295 - 306 (1986)
The compound (μ-Se)(η5-CpercentH5)Fe(CO)2>2 (1) has labile metal-selenium bonds and therefore undergoes insertion and metathesis reactions.Thus, reaction with elemental selenium gives the novel FeSeSeFe chain-type complex (μ,η1:η1-Se2)5-CpercentHpercent)Fe(CO)2>2 (2).Both compounds 1 and 2 react with the homodinuclear chromium complex 5-C5H5)Cr(CO)3>2 with formation of the heterodinuclear derivatives of composition (η5-C5H5)2CrFe(CO)5 (3; single-crystal X-ray structure: d(Cr-Fe) 290.1(1) pm) and (μ-Se2)5-C5H5)2CrFe(CO)4> (4).The latter compound exhibits a diselenido bridge ligand in η1:η2-coordination (single-crystal X-ray structure: d(Cr-Se) 249.5(2) and 255.5(2) pm, d(Fe-Se) 238.9(2), d(Se-Se) 229.7(1) pm) and can also be obtained by treatment of the chromium complex 3 with elemental selenium.
Organic Chemistry of Dinuclear Metal Centres. Part 5. Generation of Hydrocarbons from Methylene Chains linking Two Metal Centres. Evidence for a Dimetallacycle Intermediate
Cooke, Michael,Forrow, Nigel J.,Knox, Selby A. R.
, p. 2435 - 2440 (1983)
The hydrocarbon products of the thermal and photochemical decompositions of the complexes 1M2(CO)2(η-C5H5)> (M1=M2=Fe, n=3-5; M1=M2=Ru, n=3 or 4; M1=Fe, M2=Ru, n=3) have been determined and the results interpreted in terms of a transient dimetallacycle which undergoes decomposition via β-elimination and reductive elimination processes.Decomposition of the compounds containing three-carbon bridges yields cyclopropane and propene in a ratio strongly dependent upon the identity of the metal atoms and the conditions, factors which are rationalised by the proposed mechanism.But-1-ene, and cis- and trans-but-2-ene are obtained from the decomposition of complexes containing four-carbon chains, but only but-1-ene and trans-but-2-ene are produced from the thermolysis of Fe(CO)2(η-C5H5)>.This is attributed to a methyl-substituted dimetallacyclopentane intermediate adopting for steric reasons a conformation which does not allow the formation of cis-but-2-ene.The low proportion of but-1-ene can also be traced to crowding in the dimetallacyle.Pentane is preferetially evolved from Fe(CO)2(η-C5H5)>, with smaller amounts of pent-1-ene, and cis- and trans-pent-2-ene, interpreted as due to a predominantly radical mechanism for the decomposition of this compound.The organometallic products of the decompositions are the dimers (M=Fe or Ru) and, where appropriate, those of the subsequent photolysis of .Carbon-carbon bond fission occurs on heating Ru(CO)2(η-C5H5)> with Me3NO in tetrahydrofuran, giving a low yield of .
Spectroscopic Evidence for the Formation of Tri-μ-carbonyl-bis-5-cyclopentadienyl)iron> on Photolysis of Bis5-cyclopentadienyl)iron> in Low Temperature Matrices
Hooker, Richard H.,Mahmoud, Khalil A.,Rest, Antony J.
, p. 1022 - 1024 (1983)
Photolysis of 5-C5H5)Fe(CO)2>2> in CH4 (12 K) and polyvinyl chloride film (12-77 K) matrices leads to the formation of a novel species proposed, on the basis of i.r. evidence including 13CO enrichment and u.v.-visible spectra, to be the CO-bridged dimer 5-C5H5)Fe>2>.
Organic chemistry of Dinuclear Metal Centres. Part 8. Organo-Iron-Ruthenium Chemistry. X-Ray Structure of trans-
Gracey, Benjamin,Knox, Selby A. R.,Macpherson, Kirsty A.,Orpen, Guy A.,Stobart, Stephen
, p. 1935 - 1944 (1985)
The iron-ruthenium complex is obtained in 60 percent yield from the reaction of Na with .In the solid state a trans- structure has been established by X-ray diffraction.Crystals are monoclinic, space group P21/c (no. 14), with Z=2 in a unit cell for which a=7.064(2), b=12.518(3), c=8.011(2) Angstroem, and β=106.23(2) deg.The structure was solved by heavy-atom methods and refined to R 0.0275 (R' 0.0313) for 1532 independent intensities.The molecule is disordered about a centre of inversion at the mid-point of the metal-metal bond, each metal site being occupied by half an iron and half a ruthenium atom, with an iron-ruthenium bond length of 2.626(1) Angstroem.In solution the cis- isomer is dominant, and shown by 13C n.m.r. to be undergoing cis trans isomerisation with bridge terminal carbonyl exchange at room temperature, but to be static at -80 deg C.The complex is an excellent precursor of organo-iron-ruthenium chemistry.Treatment with alkynes R1C2R2 (R1 = R2 = H, Me, or Ph, R2 = H) under u.v. irradiation gives complexes 1CR2>(η-C5H5)2> in 20-65 percent yield as a result of alkyne-CO linkage.This link in the complexes derived from ethyne, propyne, and but-2-yne is broken upon protonation, generating μ-vinyl cations 1=CHR2)(η-C5H5)2>+ (R1 = R2 H or Me; R1 = H, R2 = Me).These are attacked by hydride at the β carbon of the μ-vinyl to give μ-alkylidene complexes 1R2)(μ-C5H5)2> (R1 = H, R2 = Me, Et; R1 = Me, R2 = Et).Reaction of (η-C5H5)2> with Ph3P=CHR or CH(CO2Et)N2 in boiling toluene also gives μ-alkylidene complexes (R = H, Me, or CO2Et) in good yield, through ready displacement of diphenylacetylene.The μ-CH2 complex is best obtained (75 percent) by trating with LiBHEt3 then water, and in a related manner sequential addition of methyl-lithium, HBF4*OEt2, and NaBH4 affords .Under u.v. irradiation alkynes react with μ-alkylidene complexes 1)(η-C5H5)2> to give products of alkyne-alkylidene linking 3CR2CR1)(η-C5H5)2> (R1 = H or Me, R2 = R3 = H, Me, Ph, or CO2Me; R1 = H or Me, R2 = Me or Ph, R3 = H).These exist as non-interconverting isomers in which the new C3 ligand is either bound ? to iron and and ?, η2 to ruthenium or vice versa.The scope of organo-iron-ruthenium chemistry closely resembles that of the di-iron system but it is apparent that in reactivity terms there is an order: FeRu > Fe2 > Ru2.
Chemical and structural effects of bulkness on bent-phosphinidene bridges: Synthesis and reactivity of the diiron complex [Fe2Cp 2{μ-P(2,4,6-C6H2tBu 3)}(μ-CO)(CO)2]
Alvarez, M. Angeles,Garcia, M. Esther,Gonzalez, Rocio,Ramos, Alberto,Ruiz, Miguel A.
, p. 1875 - 1878 (2010)
The steric pressure introduced by the 2,4,6-C6H2 tBu3 group (R*) in the complex [Fe 2Cp2(μ-PR*)(μ-CO)(CO)2] (Cp = η5-C5H5) has pronounced effects
