Zur reaktion von metall-koordiniertem kohlenmonoxid mit yliden: XI. Einige neuartige η1-vinyl-komplexe des eisens durch deprotonierung kationischer carbenkomplexe mit trimethyl(methylen)phosphoran

Novel η¹-vinyl complexes of the type Cp(CO)(L)FeC(OMe)C(R)R′ (R = R′ = H, Me; R = H, R′ = Me; L = Me₃P, Ph₃P) are obtainied via methylation of the acyl complexes Cp(CO)(L)FeC(O)R (R = Me, Et, i-Pr) with MeOSO₂F and subsequent deprotonation of the resulting carbene complexes [Cp(CO)(L)FeC(OMe)R]SO₃F with the phosphorus ylide Me₃PCH₂. The same procedure can be applied for the synthesis of the pentamethylcyclopentadienyl derivative C₅Me₅(CO)(Me₃P)FeC(OMe)CH₂, while treatment of the hydroxy or siloxy carbene complexes [Cp(CO)(L)FeC(OR)Me]X (R = H, Me₃Si; X = SO₃CF₃) with Me₃CH₂ results in the transfer of the oxygen bound electrophile to the ylidic carbon. Some remarkable spectroscopic properties of the new complexes are reported.     

Dictionary of organometallic compounds : (J. Buckingham,Executive Editor), Chapman and Hall,London, New York,and Toronto, 1984, 3232 pages (in three volumes), £575. ISBN 0-412-24710-0.

[C₅H₅Fe(CO)₂THF]BF₄ reacts with freshly prepared Me₃SbSe₂ to give the stable complex [C₅H₅Fe(CO)₂(Me₃SbSe)]BF₄ and red selenium.     

Zur reaktion von metall-koordiniertem kohlenmonoxid mit yliden: XXI. Ambidentes verhalten von eisenacyl-phosphor-yliden gegenüber methylfluorsulfonsäureester: Umwandlung in eisenacyl-phosphoniumsalze oder β-phosphoniovinyl- eisenkomplexe

]The reaction of the acyliron phosphorus ylide Cp(CO)₂FeC(O)CHPMe₃ with MeOSO₂F yields the acyliron phosphonium salt [Cp(CO)₂FeC(O)C(Me)- HPMe₃]SO₃F, while Cp(CO)₂FeC(O)C(Me)PEt₃ undergoes exclusively O-alkylation to the complex salt [Cp(CO)₂FeC(OMe)C(Me)PEt₃]SO₃F, (A). The acyliron ylides Cp(CO)₂FeC(O)C(R)PR₃ (R  R′  Me; or R  H, R′  Et) are converted to a mixture of the O- and C-methylated products. According to spectroscopic data and X-ray diffraction analysis of A the O- alkylation products have to be described as phosphoniovinyliron complexes.     

Phosphenium-übergangsmetallkomplexe: XX. Stabilisierung von mesitylphosphiniden durch ein Cp(CO)2W- und ein Cp(CO)2 Fe-Fragment

The reaction of the secondary metallo-phosphanes Cp(CO)₂(L)W-PH(Mes) (L  CO, PMe₃) (1a,b) with the iron complex [Cp(CO)₃Fe]BF₄ (2) or Cp(CO)2Fe-I (3), respectively, affords the ferrio(wolframio)phosphonium salts [Cp(CO)₂(L)W-P(Mes)-Fe(CO)₂Cp]X (X  I (4a), BF₄ (4b). Deprotonation of 4a, b with DBU results, in both cases, in the selective formation of a WP bond owing to additional CO- or Me₃P-elimination to give the phosphinidene complex Cp(CO)₂WP(Mes)-Fe(CO)₂Cp (6).     

Zur Reaktion von Metall-koordinierten Kohlenmonoxid mit Yliden XXII. Bis(diphenylphosphino)methanid-Eisen-Komplexe Cp(L)Fe(Ph2PCHPPh2) (L = CO,Me3P)

The reaction of [Cp(CO)(dppm)Fe]BF₄ (1a) with the phosphorus ylide Me₃PCH₂ yields the novel bis(phosphino)methanideiron complex Cp(CO)Fe(Ph₂PCHPPh₂) (2), which upon photolysis in the presnece of Me₃P is converted into Cp(Me₃P)Fe(Ph₂PCHPPh₂ (3). Reaction of 2 with MeOSO₂CF₃ gives a mixture of the iron salts [(Cp(CO)Fe(Ph₂PCR(R′)PPh₂)]CF₃SO₃ (R = R′ = H (1b), R = R′ = Me (6) and R = H, R′ = Me (syn/anti-4)).     

Basische Metalle. XXIV [1]. Ein- und zweikernige Cobaltthiolato-Komplexe aus Disulfiden. Spaltung einer S–S-Bindung durch eine Metall-Base

Basic metals. XXIV. Mono- and dinuclear cobaltthiolato complexes obtained from disulfides. Splitting of a S? S bond by a metal base The dinuclear complex C₅H₅(PMe₃)Co(μ-CO)₂Mn(CO)C₅H₄Me ( 3 ) reacts with the disulfides S₂R₂ (R ? Ph, CH₂Ph) by splitting of the sulfur-sulfur bond to form C₅H₅(PMe₃)Co(SR)₂ ( 4, 5 ). From 3 and S₂Me₂ a mixture of C₅H₅(PMe₃)Co(SMe)₂ ( 6 ) and [C₅H₅Co(μ-SMe)]₂ ( 7 ) is obtained. The synthesis of C₅H₅(PMe₃)Co(SCF₃)₂ ( 8 ) succeeds by treating 3 with N(SCF₃)₃. Whereas the reactions of 4 and 5 with MeI lead to the complex C₅H₅(PMe₃)CoI₂ ( 9 ), the dinuclear complex [C₅H₅(PMe₃)Co(μ-SPh)]₂(BF₄)₂ ( 11 ) is formed from 4 and [OMe₃]BF₄. The reactions of 11 with L = PMe₃ and P(OMe)₃ produce the compounds [C₅H₅Co(PMe₃)(L)SPh]BF₄ ( 12, 13 ), which react with [OMe₃]BF₄ to yield [C₅H₅Co(PMe₃)(L)(MeSPh)](BF₄)₂ ( 14, 15 ).     

Reactions of manganese π-acetylenic, η-vinylidenic,and η-allenylidenic complexes with Fe2(CO)9. Crystal and molecular structure of Cp(CO)2Mn(μ2-CCHCOOCH3)Fe(CO)4

The interaction between Cp(CO)₂Mn(CCHCOOMe) (I), Cp(CO)₂Mn(π-HCCCOOMe) (II), Cp(CO)₂Mn(CCCPh₂) (III), and Fe₂(CO)₉ in hexane gives rise to the complexes Cp(CO)₂Mn(μ²-CCHCOOMe)Fe(CO)₄ (IVa,b) and Cp(CO)₂Mn(μ²-CCCPh₂)Fe(CO)₄ (VIII). The structure of IVb was determined by X-ray analysis. This compound is a binuclear complex with the Fe(CO)₄ and Cp(CO)₂Mn fragments linked by a FeMn bond and a carbomethoxyvinylidenic ligand. Compound IVa is a geometrical isomer of IVb.     

Unsymmetrische(Rh—Rh)-zweikernkomplexe mit 34 valenzelektronen: Synthese und eigenschaften von C5Me5(L)Rh(μ-CO)2RhC5Me5

[C₅Me₅Rh(μ-co)]₂ reacts with phosphines (PMe₂H, PMe₃) and trimethylphosphite to give the binuclear complexes C₅Me₅(L)Rh(μ-CO)₂RhC₅Me₅ which have been characterised by elemental analyses, mass spectra,¹H and ³¹P NMR data. They are surprisingly inert toward an excess of L and do not react to give the mononuclear compounds C₅Me₅Rh(CO)L. These are obtained in good yields from C₅Me₅Rh(CO)₂ and L where L is PMe₂H, P(OMe)₃, PEt₃, P(OEt)₃ and PMe₂Ph.     

Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe. VIII. Zweikernige Cobaltkomplexe mit dem Dianion des Bis(cyclopentadienyl)methans und des Bis(tetramethylcyclopentadienyl)dimethylsilans als Brückenliganden

Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes. VIII. Dinuclear Cobalt Complexes with the Dianion of Bis(cyclopentadienyl)methane and Bis(tetramethylcyclopentadienyl)dimethylsilane as Bridging Ligands The dinuclear cobalt complex [CH₂(C₅H₄)₂][Co(CO)₂]₂ ( 4 ) which is obtained from [Co(CO)₄I] ( 2 ) and Li₂[CH₂(C₅H₄)₂] ( 3 ) in 75% yield reacts with PMe₃, PiPr₃, P₂Me₄, Me₂PCH₂CH₂PMe₂ and (EtO)₂POP(OEt)₂, to the compounds 5–9 substituting one CO ligand per cobalt atom. Oxidative addition of CH₃I to [CH₂(C₅H₄)₂][Co(CO)(PMe₃)]₂ ( 5 ) leads to the formation of the dinuclear cobalt(III) complex [CH₂(C₅H₄)₂][Co(COCH₃)(PMe₃)I]₂ ( 11 ). The reaction of 4 with iodide generates [CH₂(C₅H₄)₂][Co(CO)I₂]₂ ( 12 ) which with PMe₃, P(OMe)₃, P(OiPr)₃, and CNMe reacts under CO substitution to [CH₂(C₅H₄)₂][Co(L)I₂]₂ ( 13–16 ) and with PMe₂H to {[CH₂(C₅H₄)₂][Co(PMe₂H)₃]₂}I₄ ( 17 ). The electrophilic addition reactions of NH₄PF₆ and CH₃I to [CH₂(C₅H₄)₂][Co(PMe₃)₂]₂ ( 20 ) produce the complex salts {[CH₂(C₅H₄)₂][CoR(PMe₃)₂]₂}X₂ ( 21 : R = H; 22 : R = CH₃). From 22a (X = I) and LiCH₃ the dinuclear tetramethyldicobalt compound [CH₂(C₅H₄)₂] · [Co(CH₃)₂(PMe₃)]₂ ( 23 ) is obtained which further reacts, via the intermediate 24 , to the chiral complex {[CH₂(C₅H₄)₂] · [CoCH₃(PMe₃)P(OMe)₃]₂}(PF₆)₂ ( 25 ). The reaction of 20 with C₂(CN)₄ and E- or Z-C₂H₂(CO₂Me)₂ gives the olefin(trimethylphosphine) cobalt(I) derivatives 26 und 27 . The synthesis of the dinuclear compounds 31–38 with [Me₂Si(C₅Me₄)₂]^2? as the bridging unit is also described.     

Aromaten(phosphan)metall-komplexe: X. Protonierungsreaktionen der dimethylruthenium(II)-verbindungen C6Me6Ru(CH3)2PR3 und eine metallzentrierte bildung von 2-styryldiphenylphosphan

The compounds C₆Me₆Ru(CH₃)₂PR₃ (I, II) react with HBF₄/OEt₂ in the presence of CO or C₂H₄ to give the arene(methyl)ruthenium(II) complexes [C₆Me₆RuCH₃(CO)PRh₃]BF₄ (IV) and [C₆Me₆RuCH₃(C₂H₄)PP₃]BF₄ (V, VI), respectively. The hydrido(2-styryldiphenylphosphane) complex [C₆Me₆RuH(PPh₂C₆H₄CHCH₂)]BF₄ (VII) is formed from V (R = Ph) at room temperature by elimination of CH₄ and formation of a new CC bond. The reaction of I (R = Ph) with 50% HBF₄/H₂O in propionic anhydride gives the compound [C₆Me₆Ru(OCOEt)PPh₃]BF₄ (III) in which the propionate anion is coordinated as a chelate ligand.     

Cyclopentadienyleisen-komplexe mit P(OR)3-liganden; Synthese und spektroskopische charakterisierung

Reactions of reactive cyclopentadienyliron complexes C₅H₅Fe(CO)₂I, [C₅H₅Fe(CO)₂THF]BF₄, [C₅H₅Fe(CO)((CH₃)₂S)₂]BF₄ and [C₅H₅Fe(p-(CH₃)₂C₆H₄)]PF₆ with P(OR)₃ as ligands (R = CH₃, C₂H₅, i-C₃H₇ and C₆H₅) lead to the formation of the complex compounds C₅H₅Fe(CO)_2?n(P(OR)₃)_nI and [C₅H₅Fe(CO)_3?n(P(OR)₃)_n]X (n = 1, 2 and n = 1–3, X = BF₄, PF₆). Spectroscopic investigations (IR, ¹H, ¹³C and ³¹P NMR) indicate an increase of electron density on the central metal with increasing substitution of CO groups by P(OR)₃ ligands. The stability of the compounds increase in the same way.     

Isocyanide insertion reaction in alkylcomplexes of iron: A dihaptoiminoacyl derivative of iron (II)

The dihaptoiminoacyl complex [Fe(CO)₂ (PMe₃)₂(η²CMeNCMe₃)]⁺ I^? was obtained by reaction of [Fe(CO)₂(PMe₃)₂ MeI] and tertbutylisocyanide. The structure of the complex was determined by an X-ray structure analysis.     

Transition Metal Substituted Phosphanes: Synthesis,Reactivity and Pyramidal Inversion

Abstract

The synthesis of transition metal substituted phosphanes C₅H₅(CO)₂M-PPh₂, C₅H₅(CO)₂(Me₃P)M-PPh₂ (M [dbnd] Mo, W) and C₅H₅(CO)(Me₃P)FePPhR (R [dbnd] Me, Ph) is described as well as their reactivity towards a series of electrophilic and oxidizing reagents.     

Synthese und Reaktivität von Silicium-übergangsmetall-Komplexen: XXI. Ferrio-azidosilane and Ferriosilyl-iminophosphorane

Reaction of the ferriochlorosilanes R₅C₅(CO)₂FeSiR′_3-nCl_n (1a–1f) with sodium azide in tetrahydrofuran yields the ferrio- (mono-, bis-, and tris-azido)silanes R₅C₅(CO)₂FeSiR′_3-n(N₃)_n (R = H, Me; R′ = Me, H; n = 1–3) (2a–2f). CCl₄ converts Cp(CO)₂FeSiMe(H)N₃ (2a) into the ferrioazido(chloro)silane Cp(CO)₂-FeSiMe(Cl)N₃ (3). Treatment of 2d, 2f with Me₃P results in the formation of the ferriosilyl-iminophosphoranes Cp(CO)₂FeSi(N₃)(R)NPMe₃ (R = Me, N₃), (4a, 4b) by N₂ elimination.     

Zur reaktion von metall-koordiniertem kohlenmonoxid mit yliden: XII. Eisenkomplexe mit η1-koordinierter vinylgruppe: spontane zweif achmethylierung des β-kohlenstoffs mit methyliodid oder methylfluorsulfonsäureerster

The reaction of vinyl complexes Cp(CO)(R₃P)FeC(OMe)CH₂ (R  Me, R  Ph) with the methylating reagents MeX (X  OSO₂F, I) in the molar ratio 1/1 affords a mixture of the carbene complexes [Cp(CO)(R₃P)FeC(OMe)R]X (R  Me, Et, i-Pr). Their formation is explained via a series of acid/base equilibria established between vinyl and carbene complexes.     

Reactions of metal carbonyl derivatives : XIV. Bridged phosphido derivatives of iron and ruthenium

The tertiary phosphines P(C₆H₅)₂R [RM π-C₅H₅)(CO)₂ M(π-C₅H₅(CO)₂ (M = Fe or Ru)] readily effect the displacement of the chloro group in [M′(φ-C₅H₅)(CO)₂Cl] (M′ = Fe or Ru) to give bridged cationic species of the type [MM′(φ-C₅H₅)₂(CO)₄P(C₆H₅)]⁺. Treatment of [Fe₂(CO)₉] with P(C₆H₅)₂R [RRu(φ-C₅H₅)(CO)₂] leads to the formation of the neutral mixed-metal derivatives [FeRu(φ-C₅H₅)(CO)₆P(C₆H₅)₂] and [FeRu(φ-C₅H₅)(CO)₅P(C₆H₅)₂].     

Synthesis of alkene- and alkyne-pentamethylcyclopentadienyl dicarbonyliron complexes via the aquo derivative [Fe(η-C5Me5)(CO)2(OH2)]+BF4-; crystal structure of the ruthenium analogue

[Fe(η-C₅Me₅)(CO)₂(OH₂)]⁺ BF₄^- (2a) reacts with alkenes and alkynes to give the new complexes [Fe(η-C₅Me₅)(CO)₂(alkene)]⁺ BF₄^- and [Fe(η-C₅Me₅)(CO)₂(alkyne)]⁺ BF₄^-. The crystal structure of the ruthenium analogue [Ru(η-C₅Me₅)(CO)₂(OH₂)]⁺ CF₃SO₃^- (2b) is described.     

Basische metalle : XX. Synthese und reaktivität von C6Me6Ru(CO)PMe3. Ein stabiler aromaten-ruthenium(0)-carbonyl-komplex

Treatment of [C₆Me₆RuCl₂]₂ with carbon monoxide gives C₆Me₆Ru(CO)Cl₂ (II) which reacts with PMe₃ in the presence of NH₄PF₆ to form [C₆Me₆Ru(CO)(PMe₃)Cl]PF₆ (III). Reduction of the cation of III with NaC₁₀H₈ in THF yields C₆Me₆Ru(CO)PMe₃ (IV) which is the first stable mononuclear areneruthenium(0) carbonyl complex. IV reacts with CF₃COOH/NH₄PF₆ and MeI/NH₄PF₆ to give the stable salts [C₆Me₆RuH(CO)PMe₃]PF₄ (V) and [C₆Me₆RuCH₃(CO)PMe₃]PF₆ (VI).     

1-Alkoxy-2-azaallenyl-komplexe von chrom und wolfram

The successive reaction of (CO)₆M with Na[NCR₂¹] and [Et₃O]BF₄ yields (CO)₅M[C(NCR₂¹)OEt] (II: M = Cr; III: M = W; CR₂¹ = C(C₆H₄Br-p)₂ (a), CPh₂ (b), C(C₆H₄OMe-p)₂ (c), C(C₆H₄)₂O (d), CBu₂^tt (e)). Hexacarbonyltungsten, (CO)₆W, reacts with Na[NCPh₂] and MeOSO₂F to give (CO)₅W[C(NCPh₂) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me₃),C,N,C(Me₃) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.     

Metallkomplexe mit verbrückenden dimethylphosphidoliganden: VI. Zweikernkomplexe mit substituierten vinyldimethylphosphan-brückenliganden durch templatsynthese aus [(C5H5Co)2(μ-PMe2)2(μ-H)]+ und alkinen. Die kristallstruktur von [(C5H5Co)2(μ-PMe2)(μ-η4-Me2PC(CO2Me)CHC(OMe)O)]BF4

The hydrido-bridged dinuclear complex [(C₅H₅CO)₂(μ-PMe₂)₂(μ-H)]BF₄ (I) reacts with C₂(CO₂Me)₂ to produce a mixture of (C₅H₅Co)₂[μ-η⁴-Me₂PC(CO₂Me)C(CO₂Me)PMe₂] (II) and [(C₅H₅Co)₂(μ-PMe₂)(μ-η⁴-Me₂PC(CO₂Me)-CHC(OMe)O)]BF₄ (III). The X-ray structural analysis of III reveals that besides a dimethylphosphido bridge the cation contains a substituted vinyldimethylphosphine ligand which behaves as a 6-electron donor group and is coordinated via phosphorus and oxygen to the first cobalt and via the CC bond the second cobalt atom. The reactions of I with HC₂CO₂Me and CH₃C₂CO₂Me also give mixtures of products which contain the neutral component, (C₅H₅Co)₂[μ-η⁴-Me₂PCRC(CO₂Me)PMe₂] (IV: R  H; VII: R  CH₃), i.e., the structural analogue of II. The ionic products V, VI (obtained from HC₂CO₂Me) and VIII, IX (obtained from CH₃C₂CO₂Me) have been characterized by IR and NMR spectroscopy. {(C₅H₅Co)₂[μ-η⁴-PMe₂C(CH₃)C(CO₂Me)PMe₂](μ-H)}BF₄ (VIII) has independently been prepared by treatment of VII with HBF₄.