Crystallographic report: 1,3‐Bis[(trimethylsilylmethyl)dichlorostannyl]propane, [(Me3SiCH2)Cl2Sn]2(CH2)3

The dinuclear molecule of [(Me₃SiCH₂)Cl₂Sn]₂(CH₂)₃ adopts an extended conformation and features distorted tetrahedral tin centres, with the greatest distortion manifested in the C? Sn? C angles of approximately 128 °. The distortions are ascribed to the influence of intermolecular Sn···Cl interactions. Copyright © 2002 John Wiley & Sons, Ltd.     

Atmospheric chemistry of n‐CH3(CH2)xCN (x = 0–3): Kinetics and mechanisms

Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure the kinetics of the reaction of n‐CH₃(CH₂)_xCN (x = 0–3) with Cl atoms and OH radicals: k(CH₃CN + Cl) = (1.04 ± 0.25) × 10⁻¹⁴, k(CH₃CH₂CN + Cl) = (9.20 ± 3.95) × 10⁻¹³, k(CH₃(CH₂)₂CN + Cl) = (2.03 ± 0.23) × 10⁻¹¹, k(CH₃(CH₂)₃CN + Cl) = (6.70 ± 0.67) × 10⁻¹¹, k(CH₃CN + OH) = (4.07 ± 1.21) × 10⁻¹⁴, k(CH₃CH₂CN + OH) = (1.24 ± 0.27) × 10⁻¹³, k(CH₃(CH₂)₂CN + OH) = (4.63 ± 0.99) × 10⁻¹³, and k(CH₃(CH₂)₃CN + OH) = (1.58 ± 0.38) × 10⁻¹² cm³ molecule⁻¹ s⁻¹ at a total pressure of 700 Torr of air or N₂ diluents at 296 ± 2 K. The atmospheric oxidation of alkyl nitriles proceeds through hydrogen abstraction leading to several carbonyl containing primary oxidation products. HC(O)CN, NCC(O)OONO₂, ClC(O)OONO₂, and HCN were identified as the main oxidation products from CH₃CN, whereas CH₃CH₂CN gives the products HC(O)CN, CH₃C(O)CN, NCC(O)OONO₂, and HCN. The oxidation of n‐CH₃(CH₂)_xCN (x = 2–3) leads to a range of oxygenated primary products. Based on the measured OH radical rate constants, the atmospheric lifetimes of n‐CH₃(CH₂)_xCN (x = 0–3) were estimated to be 284, 93, 25, and 7 days for x = 0,1, 2, and 3, respectively.     

Organometallic Polyelectrolytes: Synthesis,Characterization and Layer‐By‐Layer Deposition of Cationic Poly(ferrocenyl(3‐ammoniumpropyl)‐methylsilane)

The water soluble poly(ferrocenylsilane) polycation, poly(ferrocenyl(3‐ammoniumpropyl)methylsilane), was synthesized by transition metal‐catalyzed ring‐opening polymerization of the novel [1]ferrocenophane Fe(η‐C₅H₄)₂SiCH₃(CH₂)₃Cl and by subsequent side group modification. Amination of the chloropropyl moieties using potassium 1,1,3,3‐tetramethyldisilazide followed by acidic hydrolysis produced the polycation. The polycation was employed together with poly(sodium vinylsulfonate) in the electrostatic layer‐by‐layer self‐assembly process to form organometallic multilayers on quartz. The multilayer fabrication process was monitored using UV/Vis absorption spectroscopy and XPS.     

Synthesis and molecular structure of chlorotris(trimethylsilylmethyl)trimethylsilyl-methylidyne rhenium(VII)

The complex Re(CSiMe₃)(CH₂SiMe₃)₃Cl has been isolated as yellow crystals in low yield from the reaction of ReCl₄(THF)₂ with Me₃SiCH₂MgCl and characterised by X-ray crystallography. The molecule has a trigonal bipyramidal geometry with the alkylidyne and chlorine ligands axial.     

Organometallic Compounds of the Lanthanides. 157 [1] The Molecular Structure of Tris(trimethylsilylmethyl)samarium, ‐erbium, ‐ytterbium,and ‐lutetium

SmCl₃ reacts with Me₃SiCH₂Li in THF yielding Sm(CH₂SiMe₃)₃(THF)₃ ( 1 ). The single crystal X‐ray structural analyses of 1 , Er(CH₂SiMe₃)₃(THF)₂ ( 2 ), Yb(CH₂SiMe₃)₃(THF)₂ ( 3 ), and Lu(CH₂SiMe₃)₃(THF)₂ ( 4 ) show the Sm atom in a fac‐octahedral coordination and the heavier lanthanides Er, Yb, and Lu trigonal bipyramidally coordinated with the three alkyl ligands in equatorial and two THF molecules in axial positions.     

Kinetics of the reactions of chlorine atoms with CH3ONO and CH3ONO2

The kinetics of the reactions of Cl atoms with CH₃ONO and CH₃ONO₂ have been studied using relative rate techniques. In 700 Torr of nitrogen diluent at 295 ± 2K, k(Cl + CH₃ONO) = (2.1 ± 0.2) × 10⁻¹² and k(Cl + CH₃ONO₂) = (2.4 ± 0.2) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹. The result for k(Cl + CH₃ONO₂) is in good agreement with the literature data. The result for k(Cl + CH₃ONO) is a factor of 4.5 lower than that reported previously. It seems likely that in the previous study most of the loss of CH₃ONO which was attributed to reaction with Cl atoms was actually caused by photolysis leading to an overestimate of k(Cl + CH₃ONO). © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 357–359, 1999     

Zweikernige Palladium(II)‐, Platin(II)‐ und Iridium(III)‐Komplexe von Bis[imidazol‐4‐yl]alkanen

Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH₂)_n bridged imidazoles L(CH₂)_nL, n = 3–6) with chloro bridged complexes [R₃P(Cl)M(μ‐Cl)M(Cl)PR₃] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl₂(R₃P)M–L(CH₂)_nL–M(PR₃)Cl₂] 1 – 17 . The structures of [Cl₂(Et₃P)Pd–L(CH₂)₃L–Pd(PEt₃)Cl₂] ( 1 ), [Cl₂(Bu₃P)Pd–L(CH₂)₄L–Pd(PBu₃)Cl₂] ( 10 ), [Cl₂(Et₃P)Pd–L(CH₂)₅L–Pd(PEt₃)Cl₂] ( 3 ), [Cl₂(Et₃P)Pt–L(CH₂)₃L–Pt(PEt₃)Cl₂] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl₂(Cp*)Ir–L(CH₂)_nL–Ir(Cp*)Cl₂] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)₂Ir(Cl)Cp*] and the methylene bridged bis(imidazoles).     

An FTIR study of the Cl atom-initiated oxidation of CH2Cl2 and CH3Cl

The Cl atom-initiated oxidation of CH₂Cl₂ and CH₃Cl was studied using the FTIR method in the photolysis of mixtures typically containing Cl₂ and the chlorinated methanes at 1 torr each in 700 torr air. The results obtained from product analysis were in general agreement with those reported by Sanhueza and Heicklen. The relative rate constant for the Cl atom reactions of CH₂Cl₂ and CH₃Cl was determined to be k(Cl +CH₃Cl)/k(Cl + CH₂Cl₂) = 1.31 ± 0.14 (2σ) at 298 ± 2 K.     

Ionic Transformations in Extremely Nonpolar Fluorous Media: Easily Recoverable Phase‐Transfer Catalysts for Halide‐Substitution Reactions

Solutions of the fluorous alkyl halides R_f8(CH₂)_mX (R_fn=(CF₂)_n?1CF₃; m=2, 3; X=Cl, Br, I) in perfluoromethylcyclohexane or perfluoromethyldecalin are inert towards solid or aqueous NaCl, NaBr, KI, KCN, and NaOAc. However, halide substitution occurs in the presence of fluorous phosphonium salts (R_f8(CH₂)₂)(R_f6(CH₂)₂)₃P⁺X^? (X=I ( 1 ), Br ( 3 )) and (R_f8(CH₂)₂)₄P⁺I^? (10 mol %), which are soluble in the fluorous solvents under the reaction conditions (76–100 °C). Stoichiometric reactions of a) 1 with R_f8(CH₂)₂Br and b) 3 with R_f8(CH₂)₂I were conducted under homogenous conditions in perfluoromethyldecalin at 100 °C and yielded the same R_f8(CH₂)₂I/R_f8(CH₂)₂Br equilibrium ratio (≈60:40). This shows that ionic displacements can take place in extremely nonpolar fluorous phases and suggests a classical phase‐transfer mechanism for the catalyzed reactions. Interestingly, the nonfluorous salt (CH₃(CH₂)₁₁)(CH₃(CH₂)₇)₃P⁺I^? ( 4 ) also catalyzes halide substitutions, but under triphasic conditions with 4 suspended between the lower fluorous and upper aqueous layers. NMR experiments established very low solubilities in both phases, which suggests interfacial catalysis. Catalyst 1 is easily recycled, optimally by simple precipitation onto teflon tape.     

Structural motifs of Au(I)-Cu(I) N-heterocyclic carbene halide complexes

A series of Au(I)–Cu(I) N-heterocyclic carbene (NHC) halide complexes [AuCu₂(im(CH₂py)₂)₂X]²⁺ where X?=?Cl (1), Br (2), I (3) was prepared by refluxing [AuCu₂(im(CH₂py)₂)₂(NCCH₃)₄]³⁺ with the appropriate halide in acetonitrile. The compounds were characterized by NMR, absorption, and fluorescence spectroscopy. They feature similar solution behavior and solid-state photoemissions. The solid-state structures feature a rhomboidal [AuCu₂X]²⁺ core which is influenced by the type of halide. Compared to other Au(I)–Cu(I) NHC complexes, 1–3 comprise a new structural motif containing a bridging halide. The benzimidazolium analog of 1 was also characterized crystallographically. The structure of [AuCu₂(benzim(CH₂py)₂)₂Cl]²⁺(4) features different coordination modes of the NHC ligands with the carbenic carbon bonded to both gold and copper and the pyridyl groups bonded to the same copper(I) ion.     

3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene

Rh‐containing metallacycles, [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NR)₂‐]Cl; TPA=N,N,N,N‐tris(2‐pyridylmethyl)amine have been accessed through treatment of the Rh^I ethylene complex, [(TPA)Rh(η²‐CH₂CH₂)]Cl ([ 1 ]Cl) with substituted diazenes. We show this methodology to be tolerant of electron‐deficient azo compounds including azo diesters (RCO₂N?NCO₂R; R=Et [ 3 ]Cl, R=iPr [ 4 ]Cl, R=tBu [ 5 ]Cl, and R=Bn [ 6 ]Cl) and a cyclic azo diamide: 4‐phenyl‐1,2,4‐triazole‐3,5‐dione (PTAD), [ 7 ]Cl. The latter complex features two ortho‐fused ring systems and constitutes the first 3‐rhoda‐1,2‐diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N–N coordination followed by insertion of ethylene into a [Rh]?N bond. In terms of reactivity, [ 3 ]Cl and [ 4 ]Cl successfully undergo ring‐opening using p‐toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh^III(Cl)(κ¹‐(C)‐CH₂CH₂(NCO₂R)(NHCO₂R)]OTs; [ 13 ]OTs and [ 14 ]OTs. Deprotection of [ 5 ]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end‐on coordinated diazene [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NH)₂‐]⁺ [ 16 ]Cl, a hitherto unreported motif. Treatment of [ 16 ]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NAc)₂‐]⁺, [ 17 ]Cl. Treatment of [ 1 ]Cl with AcN?NAc did not give the Rh?N insertion product, but instead the N,O‐chelated complex [(TPA)Rh^I ( κ²‐(O,N)‐CH₃(CO)(NH)(N?C(CH₃)(OCH?CH₂))]Cl [ 23 ]Cl, presumably through insertion of ethylene into a [Rh]?O bond.     

The synthesis of a cationic ylide complex of platinum(II) by the reaction of tetrakis(triphenylphosphine)platinum(O) with choloroiodomethane.

The reaction of Pt(PPh₃)₄ with CH₂Cl1 in benzene yields the cationic ylide complex $\text{cis}$-[Pt(PPh₃)₂(CH₂PPh₃)Cl]I in high yield. This complex has been converted to $\text{cis}$-[(PPh₃)₂(CH₂PPh₃)X]X (X  Br or I) by reaction with LiBr or NaI. Reaction of $\text{cis}$-[Pt(PPH₃)I]I with iodine yields $\text{cis}$-[Pt(PPh₃)₂(CH₂PPh₃)I]I₃. Nmr data are given in support of the suggested structures.     

Kinetic study of the reaction of chlorine atoms with CF3I and the reactions of CF3 radicals with O2, Cl2 and NO at 296 K

The kinetics of the gas-phase reaction of Cl atoms with CF₃I have been studied relative to the reaction of Cl atoms with CH₄ over the temperature range 271–363 K. Using k(Cl + CH₄) = 9.6 × 10^?12 exp(?2680/RT) cm³ molecule^?1 s^?1, we derive k(Cl + CF₃I) = 6.25 × 10^?11 exp(?2970/RT) in which E_a has units of cal mol^?1. CF₃ radicals are produced from the reaction of Cl with CF₃I in a yield which was indistinguishable from 100%. Other relative rate constant ratios measured at 296 K during these experiments were k(Cl + C₂F₅I)/k(Cl + CF₃I) = 11.0 ± 0.6 and k(Cl + C₂F₅I)/k(Cl + C₂H₅Cl) = 0.49 ± 0.02. The reaction of CF₃ radicals with Cl₂ was studied relative to that with O₂ at pressures from 4 to 700 torr of N₂ diluent. By using the published absolute rate constants for k(CF₃ + O₂) at 1–10 torr to calibrate the pressure dependence of these relative rate constants, values of the low- and high-pressure limiting rate constants have been determined at 296 K using a Troe expression: k₀(CF₃ + O₂) = (4.8 ± 1.2) × 10^?29 cm⁶ molecule^?2 s^?1; k_∞(CF₃ + O₂) = (3.95 ± 0.25) × 10^?12 cm³ molecule^?1 s^?1; F_c = 0.46. The value of the rate constant k(CF₃ + Cl₂) was determined to be (3.5 ± 0.4) × 10^?14 cm³ molecule^?1 s^?1 at 296 K. The reaction of Cl atoms with CF₃I is a convenient way to prepare CF₃ radicals for laboratory study. © 1995 John Wiley & Sons, Inc.     

Complexes of group IIb metals with dithio oxamides—II. Vibrational analysis of ZnLX2(X = Cl,Br, I) complexes

With dithiooxamides, Zn(II) in acid media forms distorted tetrahedral complexes, which behave as non-electrolytes. The ligands act as bidentates with S, S coordination.A thorough vibrational analysis has been performed for the Zn(CH₃ NHCSCSNHCH₃)X₂(X = Cl, Br, I) and for the Zn[(CH₃)₂NCSCSN(CH₃)₂]X₂(X = Cl, Br, I) complexes.     

Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η2‐Allene‐Coordinated Complexes

The reactions of phosphonium‐substituted metallabenzenes and metallapyridinium with bis(diphenylphosphino)methane (DPPM) were investigated. Treatment of [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl₂(PPh₃)₂]Cl with DPPM produced osmabenzenes [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl₂{(PPh₂)CH₂(PPh₂)}]Cl ( 2 ), [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 3 ), and cyclic osmium η²‐allene complex [Os{CH?C(PPh₃)CH?(η²‐C?CH)}Cl₂{(PPh₂)CH₂(PPh₂)}₂]Cl ( 4 ). When the analogue complex of osmabenzene 1 , ruthenabenzene [Ru{CHC(PPh₃)CHC(PPh₃)CH}Cl₂(PPh₃)₂]Cl, was used, the reaction produced ruthenacyclohexadiene [Ru{CH?C(PPh₃)CH?C(PPh₃)CH}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 6 ), which could be viewed as a Jackson–Meisenheimer complex. Complex 6 is unstable in solution and can easily be convert to the cyclic ruthenium η²‐allene complexes [Ru{CH?C(PPh₃)CH?(η²‐C?CH)}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 7 ) and [Ru{CH?C(PPh₃)CH?(η²‐C?CH)}Cl₂{(PPh₂)CH₂(PPh₂)}₂]Cl ( 8 ). The key intermediates of the reactions have been isolated and fully characterized, further supporting the proposed mechanism for the reactions. Similar reactions also occurred in phosphonium‐substituted metallapyridinium [OsCl₂{NHC(CH₃)C(Ph)C(PPh₃)CH}(PPh₃)₂]BF₄ to give the cyclic osmium η²‐allene‐imine complex [OsCl₂{NH?C(CH₃)C(Ph)?(η²‐C?CH)}{(PPh₂)CH₂(PPh₂)}(PPh₃)]BF₄ ( 11 ).     

New Insights in Asymmetric Tetraorganodistannoxane Ladder Formation. A NMR‐Spectroscopic and Crystallographic study

The syntheses of the asymmetrically substituted tetraorganodistannoxanes [t‐Bu₂(X)SnOSn(Y)(CH₂SiMe₃)₂]₂ ( 1 , X = Y = OH; 2 , X = Cl, Y = OH; 3 , X = Y = Cl) are reported and their structures in solution and in the solid state are characterized by multinuclear NMR spectroscopy and single crystal X‐ray analyses. In toluene, the tetrahydroxy‐substituted derivative 1 is in equilibrium with the organotin oxides cyclo‐[t‐Bu₂Sn{OSn(CH₂SiMe₃)₂}₂O] ( 4 ), cyclo[(Me₃SiCH₂)₂Sn(OSnt‐Bu₂)₂O] ( 5 ), and cyclo‐(t‐Bu₂SnO)₃, and some additional, undefined species containing pentacoordinated tin atoms. In contrast, the dihydroxydichloro‐substituted derivative 2 is inert in solution.     

Bildung siliciumorganischer Verbindungen. 98. Umsetzung silylierter Phosphorylide mit PCl3

Formation of Organosilicon Compounds. 98. Reaction of Silylated Phosphorus Ylides with PCl₃ The reaction of Si-substituted phosphorus ylides as Me₂Si(CH₂? SiMe₂)₂C?PMe₃Br 1 , Cl₂Si(CH₂? SiCl₂)₂C?PMe₂Cl 2 , and (Cl₃Si)₂C?PMe₂Cl 3 with PCl₃ yields (Cl₂P)₂C?PMe₂Cl 5 by chlorinating cleavage of the Si-ylid-C bond. Besides 5 also (ClMe₂SiCH₂)₂SiMe₂, (Cl₃SiCH₂)₂SiCl₂, resp. SiCl₄ result from the reaction of 1, 2 and 3 with PCl₃. (Cl₂P)₂C?PMe₂Cl forms colourless crystals, mp. 84°C.     

Silicon‐ and Tin‐Containing Open‐Chain and Eight‐Membered‐Ring Compounds as Bicentric Lewis Acids toward Anions

Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me₂Si(CH₂SnMe₂X)₂ ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH₂(SnMe₂CH₂I)₂ ( 7 ), CH₂(SnMe₂CH₂Cl)₂ ( 8 ), cyclo‐Me₂Sn(CH₂SnMe₂CH₂)₂SiMe₂ ( 6 ), cyclo‐(Me₂SnCH₂)₄ ( 9 ), cyclo‐Me_(2?n)X_nSn(CH₂SiMe₂CH₂)₂SnX_nMe_(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt₄[cyclo‐ Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?F] ( 13 ), PPh₄[cyclo‐Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?Cl] ( 14 ), NEt₄[cyclo‐Me(F)Sn(CH₂SiMe₂CH₂)₂Sn(F)Me?F] ( 15 ), [NEt₄]₂[cyclo‐Cl₂Sn(CH₂SiMe₂CH₂)₂SnCl₂?2 Cl] ( 16 ), M[Me₂Si(CH₂Sn(Cl)Me₂)₂?Cl] ( 17 a , M=PPh₄; 17 b , M=NEt₄), NEt₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?F] ( 18 ), NEt₄[Me₂Si(CH₂Sn(F)Me₂)₂?F] ( 19 ), and PPh₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and ¹H, ¹³C, ¹⁹F, ²⁹Si, and ¹¹⁹Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies.     

Mechanism and characterization of alkylene‐ and p‐ethylenebenzylene‐spaced polycarbosilanes ceramic precursor synthesized by electropolymerization

An electropolymerization of haloalkylhalosilanes (Cl? R? SiCH₃Cl₂) that possess two types of electroactive sites, that is, the C? Cl and Si? Cl bond is described. The one‐pot synthesis method is shown to yield branched polycarbosilanes having a regular carbon block‐spaced silicon backbone structure. A series of branched polycarbosilanes, [? R? SiCH₃? ]_n with R being ? CH₂? , ? C₂H₄? , ? C₃H₆? , and ? CH₂? C₆H₄? C₂H₄? , have been successfully electropolymerized with M_n up to 42,600 Dalton. Experimental and simulation cyclic voltammetry of these monomers and the computational examination of their LUMOs are applied to study the electropolymerization mechanism. The results suggest that polymerization proceeds by iterating steps involving (1) electroreduction of a C? Cl bond to a carbanion, which is catalyzed by silylanion radical [Cl SiCl(CH₃)RCl] and/or Ni(0)/TDA‐1; and (2) nucleophilic attack of carbanions to Si? Cl bonds of a second monomer or oligomer to extend the polymer chain. The investigation reveals that the R spacer has a considerable impact on the polymerizability of the corresponding monomer. Such interfacial polymerization resembles a template polymerization, leading to unique microstructures that were preserved even after converted to silicon carbide ceramics at high temperatures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7677–7689, 2008     

Preparation and reactivity of the new cyclopentadienyl-bridged complex (Me2SiCH2CH2SiMe2)(C5H4Fe(CO)2)2

A new metal-metal bonded binuclear iron system [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)₂]₂ (2) has been prepared by treating two equivalents of NaCp with one equivalent of ClSi(Me)₂CH₂CH₂SiClMe₂ obtaining the intermediate (C₅H₅)Si(Me)₂CH₂CH₂Si(Me)₂(C₅H₅) which then is directly allowed to react with Fe(CO)₅ given 2 in 30% yield. From this cyclopentadienyldisilyl linked system three new binuclear irom complexes are formed. Treatment of 2 with Na/Hg in THF produced the dianion [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)₂^?]₂ which is quenched with CH₃I giving [Me₂SiCH₂CH₂SiMe₂][η⁵-C₄H₄Fe(CO)₂CH₃]₂ (4) in 76% yield. Complex 2 is oxidized with 1.2 equivalent of I₂ to give [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)₂I]₂ (5) in 85% yield. Photolysis of 5 (1 equiv.) and PPh₃ (3 equiv.) results in the formation of the bis-substituted compound [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)(PPh₃)I]₂ (6). These four new binuclear iron complexes are characterized by ¹H, ¹³C, and ³¹P NMR and IR spectroscopy.