Several new compounds of the type [CpOsH2(PPh3)2]+ X−, where X = Cl, Br, I, I3, BPh4, p-toluenesulphonate, d(+)-campho-10-sulphonate, have been obtained in the form of ion pairs or salts. The above compounds form during oxidative addition by HX acids to CpOsH(PPh)3)2. The reactions are complete ...

The cyclopentadienyl osmium(II) complexes [(η5-C5H5)Os(PPh3)2X] [X = Br (1), CH3CN (2)] reacts with sodium azide (NaN3) to yield the corresponding azido complex [(η5-C5H5)Os(PPh3)2N3] (3). This undergoes [3+2] dipolar cycloaddition reaction with activated alkynes like dimethyl and diethyl acet...

Reaction of [CpOs(PPh3)2Br] (1) with acetonitrile ligand or monodentate anions yielded complexes of the type [CpOs(PPh3)2(CH3CN)]+ (2), [CpOs(PPh3)2X], X=CN (3) and NCS (4). Treatment of 1 with NaNO2–HCl in the presence of NH4BF4 yielded the dicationic complex [CpOs(PPh3)2(NO)](BF4)2 (5). React...

The electrochemical behavior of osmociphenol (3, Oc-OH), an organometallic osmium-based anticancer drug candidate, has been investigated by cyclic voltammetry in the absence and presence of lutidine used as a base model. Osmociphenol exhibited spontaneous deprotonation of the phenol function upo...

A mixed Ullman reaction between iodoferrocene and 1,2-diiodoferrocene as well as an Ullmann reaction involving only 1,2-diiodoferrocene both produce biferrocene as well as linear 1,2-oligomeric ferrocenes, including 1,2-terferrocene, meso-1,2-quaterferrocene, dl-1,2-quaterferrocene and several i...

Racemic 2-hydroxymethyl-1-iodoferrocene (±)-1 was subjected to esterification in the presence of lipase from Candida antarctica (Novozym® 435) to afford (1S,2S)-2-acetoxymethyl-1-iodoferrocene (−)-2 having 89% ee and unreacted (1R,2R)-2-hydroxymethyl-1-iodoferrocene (+)-1 in enantiopure form. A...

A new method for the synthesis of 3-substituted-1-ferrocenyl-2-propyn-1-ones was developed involving carbonylative Sonogashira coupling of iodoferrocene with terminal acetylenes. New ferrocenyl 1,3,5-trisubstituted pyrazoles and 2,4,6-trisubstituted pyrimidines were obtained by the addition-cycl...

The synthesis of iodoferrocenes using stannylferrocenes as key intermediates is described. The method is suitable for the bulk preparation of iodoferrocenes.

The ortho-lithiation of 1,1′-dibromoferrocene is reported for the first time. The reaction is carried out using LDA at low temperature in THF to avoid metathesis. A number of electrophilic quenching reagents have been used, resulting in the formation of a new series of substituted 1,1′-dibromo...

Conformational preferences for isolated molecules of ferrocene, 1-bromoferrocene and 1,1′-dibromoferrocene were obtained by combined use of matrix-isolation infrared spectroscopy and quantum chemical calculations. Monomeric ferrocene and 1-dibromoferrocene were found to exist in a low temperatu...

The reaction of a mixture of sodium cyclopentadienide and the monolithium salt or dilithium salt of 2,2-bis(indenyl)propane with FeCl2 leads to the mononuclear complex [(η5-C5H5)Fe(η5-ind-C(CH3)2-ind)] (ind = 1-indenyl) (1) and the dinuclear complex [{(η5-C5H5)Fe(η5-ind)}2C(CH3)2] (2), respe...

The bis(indenyl) derivatives of Fe, Co, and Ni were studied by means of DFT calculations (adf program). The calculated structures were compared with the experimental ones and a good agreement was observed. While bis(indenyl)iron is an 18-electron compound, exhibiting an almost perfect η5 coordi...

The new bridged ligand (C9Me6H)2SiMe2 9 has been prepared and used to synthesise the first strained ansa-bridged bis(indenyl)iron complex Fe(η5-C9Me6)2SiMe2 11. The properties of 11 are compared with those of other SiMe2-bridged [1]-ferrocenophanes and with the unbridged analogue Fe(η5-C9Me6H)...

Several new methyl-substituted indenyl ferrocenes were prepared by metathesis reactions of the indenide (generated from the appropriate indene with BuLi) with ferrous chloride. The indenides used to prepare new ferrocenes were: 2-methyl-, 1,2-dimethyl-, 4,7-dimethyl-, 1,4,7-trimethyl-, and 1,3,4...

The reaction of [Ru3(CO)12] (1), with indene in refluxing xylene affords [{(η5-C9H7)Ru(CO)2}2] (2), in high yield. An analogous reaction of 1 with 2-phenylindene affords the expected dinuclear complex [{(η5-C9H6Ph)Ru(CO)2}2] (5), and a heptaruthenium cluster [(C9H4Ph)Ru7(μ-H)(μ-CO)2(CO)16] (...

(Indenyl)rhodacarboranes 1,2-R2-3-(η5-indenyl)-3,1,2-RhC2B9H9 (2a: R = H; 2b: R = Me) and 3-(η5-indenyl)-4-SMe-3,1,2-RhC2B9H10 (3) were synthesized by reactions of the iodide complex [(η5-indenyl)RhI2]n (1b) with Tl[Tl(η-7,8-R2-7,8-C2B9H9)] or Tl[9-SMe2-7,8-C2B9H10]. The formation of 3 is ac...

The synthesis of the bis(η5-indenyl)iron sandwich complexes (η5-1-SiMe3–C9H6)2Fe (3a), (η5-2-SiMe3–C9H6)2Fe (3b), [η5-1,2-(SiMe3)2C9H5]2Fe (4a) and [η5-1,3-(SiMe3)2C9H5]2Fe (4b), by the reaction of the appropriate lithium indenide salts [prepared from 1-SiMe3–C9H7 (2a), 2-SiMe3–C9H7 (2b...

The iron complex [(η5-indenyl)Fe(η6-indene)]+ (1) was prepared via one-pot procedure in 25% yield by reaction of FeCl3 with indenyl lithium giving Fe(η5-indenyl)2 and its subsequent protonation with CF3COOH. Cation 1 reacts with 2e ligands L (L = tBuNC, P(OMe)3, P(OEt)3, PMe(OEt)2) under visi...

The electronic interaction between the iron atom and the indenyl ligands with one and two trimethylsilyl substituents in different isomeric positions in bis(indenyl)iron has been studied using cyclic voltammetry and UV–vis spectroscopy. Results and interpretation are supported by theoretical PM...

Bis(indenyl)-rhodium and -iridium complexes [(η5-indenyl)M(η5-C9H2R5)]PF6 (2a: M = Rh, R = H; 2b: M = Ir, R = H; 3: M = Rh, R = Me) were synthesized by reactions of iodides [(η5-indenyl)MI2]n (1a,b) with indenes in the presence of AgPF6. The structures of 2aSbF6 and 2bPF6 were determined by X...