Synthesis and structural characterization of new mixed-ring indenyl derivatives of molybdenum containing phosphorus ligands

Reaction of NaBH₄ with [IndCpMo(dppe)](BF₄)₂ (1) in acetone yields [IndMo(η⁴-C₅H₆)(dppe)]BF₄ (2) quantitatively. The hydride addition takes place at the external face of the Cp ring. Dissolution of 2 in dichloromethane gives [IndMo(η⁴-C₅H₅-exo-CH₂Cl)(dppe)]BF₄, as confirmed by elemental analysis, IR and ¹H NMR spectroscopy. The similar dication [IndCpMo{P(OMe)₃}₂](BF₄)₂ (4) reacts with NaBH₄, in a solvent dependent manner. In acetonitrile, [IndMo(η⁴-C₅H₆){P(OMe)₃}₂]BF₄ (5) is obtained and in acetone a P(OMe)₃ ligand is lost resulting in the asymmetric phosphite-hydride, [IndCpMoH{P(OMe)₃}]⁺ (6). The molecular structures of [IndMo(η⁴-C₅H₆){P(OMe)₃}₂]PF₆ and [IndCpMoH{P(OMe)₃}]PF₆ were characterized by single-crystal X-ray diffraction.     

Half-sandwich and mixed-ring uranium complexes

The monocyclooctatetraene uranium complex [U(COT)(I)₂(THF)₂] (COT=η-C₈H₈; THF=tetrahydrofuran), isolated from the reaction of bis(cyclooctatetraene)uranium with iodine, is a precursor for the synthesis of the alkyl derivatives [U(COT)(CH₂Ph)₂i (HMPA) ₂], [U(COT)(CH₂SiMe₃)₂(HMPA)] (HMPA=hexamethyl phosphorous triamide) and [U(COT)CH₂SiMe₃)₃] [Li(THF)₃] and of the mixed-ring compounds [U(COT)(η-C₅R₅)(I)] (R=H or Me). The last were used to prepare the amide and alkyl complexes [U(COT)(η-C₅H₅)(N{SiMe₃}₂)] and [U(COT)(η-C₅Me₅)(CH₂SiMe₃)].     

Structural preferences of cyclopentadienyl and indenyl rings in iridium(I) carbene complexes

Cleavage of the [Ir(η⁴-COD)Cl]₂ dimer in the presence of the corresponding imidazolium salts and the strong base tBuO⁻ leads to the formation of Ir(I) derivatives of N-heterocyclic carbenes. When halide is replaced by NaCp, a mixture of [Ir(η⁴-COD)(NHC^R)(η¹-Cp)] and [Ir(η²-COD)(NHC^R)(η⁵-Cp)] is obtained. The latter is favored for R = Cy, while the former predominates for R = Me. Conversely, [Ir(η⁴-COD)(NHC^R)(η¹-Ind)] is the only product of the reaction with NaInd, despite the R substituent. DFT/B3LYP calculations confirmed that the η¹ coordination mode of the ring gives rise to the most stable structures, namely square planar complexes of 5d⁸ Ir(I). The energy of the 18 electron species containing η²-COD and η⁵-Ind or Cp is higher by 13 and 5 kcal mol⁻¹, respectively. The fluxional behaviour of indenyl, detected by NMR in the solutions of [Ir(η⁴-COD)(NHC^R)(η¹-Ind)], is associated to the low energy of the η³-Ind species required in the conversion process, and is not easily observed in the cyclopentadienyl derivatives, where a similar intermediate is disfavored.     

Cyclopentadienyl, indenyl, and fluorenyl complexes of sodium with 15-crown-5

The sodium complexes [NaC₅H₅(15-crown-5)] (1a), [NaC₉H₇(15-crown-5)] (1b), and [NaC₁₃H₉(15-crown-5)] (1c, C₅H₅=cyclopentadienyl, C₉H₇=indenyl, C₁₃H₉=fluorenyl) were synthesized from NaC₅H₅, NaC₉H₇, NaC₁₃H₉, and 15-crown-5. Single crystal X-ray diffraction analyses were carried out for all three compounds 1a, 1b, 1c, and show that monomeric units were present in the solid state with the organic aromatic anion coordinated to the sodium cation via the five-membered ring.     

The synthesis and reactivity of some indenyl and bis-indenyl ruthenium carbonyl complexes

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] (6). The indenyl ligand in compound 6 exhibits a novel bonding mode in which the benzenoid ring is μ₄,η¹:η¹:η²:η² bound to the cluster. Refluxing 1 with bis-indenyl methane affords the dinuclear complex [Ru₂(CO)₄{μ-(η⁵-C₉H₆)₂CH₂}] (7), which reacts with iodine via Ru-Ru bond cleavage to give [Ru₂I₂(CO)₄{(η⁵-C₉H₆)₂CH₂}] (8).     

Reactivity of the metal-cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds

The focus of this review concerns the reactivity patterns of metal-cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds. The advances in the metal-carbon(η⁵) insertion chemistry have demonstrated that the π-bonding character provides additional reaction opportunities which are not shown by metal-alkyl compounds and these differences are highlighted.     

Zirconium bis(indenyl) sandwich complexes with an unprecedented indenyl coordination mode and their role in the reactivity of the parent bent-metallocenes: a detailed DFT mechanistic study

The mechanisms of three closely related reactions were studied in detail by means of DFT/B3 LYP calculations with a VDZP basis set. Those reactions correspond to 1) the reductive elimination of methane from [Zr(eta5-Ind)2(CH3)(H)] (Ind=C9H7-, indenyl), 2) the formation of the THF adduct, [Zr(eta5-Ind)(eta6-Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(eta5-Ind)(eta9-Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18-electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr-bis(indenyl) species, corresponding to different spin states (S=0 and S=1), different coordination modes of the two indenyl ligands (eta5/eta9, eta5/eta5 and eta6/eta9), and three conformations for each isomer (syn, anti, and gauche). The fluxionality observed was found to occur in a mechanism involving bis(eta5-Ind) intermediates, and the calculated activation energy (11-14 kcal mol(-1)) compares very well with the experimental values. Two alternative mechanisms were explored for the reductive elimination of methane from the methyl/hydride complex. In the more favourable one, the initial complex, [Zr(eta5-Ind)2(CH3)(H)], yields [Zr(eta5-Ind)2] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable eta5/eta9-species. The overall activation energy calculated (Ea=29 kcal mol(-1)) compares well with experimental values for related species. The formation of the THF adduct follows a one step mechanism from the appropriate conformer of the [Zr(eta5-Ind)(eta9-Ind)] complex, producing easily (Ea=6.5 kcal mol(-1)) the known product, [Zr(eta5-Ind)(eta6-Ind)(thf)], a species previously characterised by X-ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal mol(-1) more stable isomer, [Zr(eta5-Ind)2(thf)], with both indenyl ligands in a eta5-coordination mode and a spin-triplet state (S=1).     

Synthesis and Structure of Lanthanide Sandwich Complexes with Mixed Cyclooctatetraenyl and Chelating Substituted‐indenyl Ligands

Two types of sandwich complexes (η⁵‐MeOCH₂CH₂C₉H₆) Ln (η⁸‐C₈H₈) (THF)_n [Ln=La (1), Nd(2), n=0; Sm(3), Dy (4) and Er (5). n = l] and (η⁵‐C₄H₇OCH₂C₉H₆)Ln(η⁸‐C₈H₈) (THF) [Ln = La (6), Nd(7). Sm(8). Dy (9) and Er (10)] were synthesized by the reactions of LnCl₃ with equivalent mole of K₂C₈H₈, followed by treatment with corresponding potassium salt of ether‐substituted indenide. The molecular structures of 3 and 8 were determined by single crystal X‐ray diffraction. (η⁵ ‐MeOCH₂CH₂C₉H₆) Sm (η⁸‐C₈H₈) (THF) (3) monoclinic. Pt₁/c, a = 1.4793(3) nm, b = 0.8716 (2) nm, c = 1.6149 (3) nm, β = 98. 17(3), V = 2.0612(7) nm³, Z = 4, R(F)=0.0362. (η⁵‐C₄H₇OCH₂C₉H₆)Sm(η⁸‐C₈H₈)(THF) (8) orthorhombic. p2₁2₁2₁. a = 0.8754(2) nm, b = 1.1000(2) nm, c = 2.3117 (5) nm, V = 2.2260(8) nm³, Z=4, R(F) =0.0497.     

Synthesis and reactivity of substituted cyclopentadienyl rhodium(I) and (III) complexes

New cyclopentadienyl derivatives of rhodium COD complexes [Cp*=C₅H₄COOCH₂CHCH₂ (1); C₅H₄CH₂CH₂CHCH₂ (2); C₅H(i-C₃H₇)₄ (3)] and carbonyl complex [Cp*=C₅H(i-C₃H₇)₄ (4)] were synthesized from [RhCl(COD)]₂ and [RhCl(CO)₂]₂. 1, 2 and 3 oxidized by iodine gave iodine bridged dimers 5, 6 and 7, respectively. Triphenyl phosphine, carbon monoxide and carbon disulfide molecules broke down the iodine bridged structure easily and produced monomer products Cp*RhI₂L [Cp*=C₅H₄COOCH₂CHCH₂, L=CS₂ (8); L=PPh₃ (9). Cp*=C₅H(i-C₃H₇)₄, L=CO (10)]. All of these new compounds were characterized by elemental analysis, ¹H NMR, IR, UV-Vis and mass spectroscopy. The crystal structure of 1 was solved in the triclinic space group with one molecule in the unit cell, the dimensions of which are a=7.082(9) Å, b=8.392(3) Å, c=13.889(5) Å, α=101.19(3)°, β=99.06(6)°, γ=105.11(5)°, and V=763(1) ų. The crystal structure of 3 was solved in the orthorhombic space group Pn21a with four molecules in the unit cell, the dimensions of which are a=9.748(3) Å, b=16.054(5) Å, and V=2319(1) ų. Least squares refinement leads to values for the conventional R₁ of 0.0251 for 1 and 0.0558 for 3, respectively. Compared to that in 1, a shorter metal-ligand bond length in 3 was observed and this is attributed to the rich electron density on Rh(I) metal center piled up by the C₅H(i-C₃H₇)₄ ligand.     

Molybdenum complexes containing substituted cyclopenta[l]phenanthrenyl ligand

The synthesis of new cyclopenta[l]phenanthrenyl complexes [(η⁵-C₁₇H₁₀Me)(η³-C₃H₅)Mo(CO)₂] and [(η⁵-C₁₇H₉(COOMe)N(CH₂)₄)(η³-C₃H₅)Mo(CO)₂] is described. Although these compounds are structural analogues their reactivity is different. Protonation of [(η⁵-C₁₇H₁₀Me)(η³-C₃H₅)Mo(CO)₂] gives a stable ionic compound [(η⁵-C₁₇H₁₀Me)Mo(CO)₂(NCMe)₂][BF₄] while its analogue containing both tertiary amino and carboxylic ester groups [(η⁵-C₁₇H₉(COOMe)N(CH₂)₄)(η³-C₃H₅)Mo(CO)₂] decomposes under the same conditions. [(η⁵-C₁₇H₁₀Me)Mo(CO)₂(NCMe)₂][BF₄] reacts with cyclopentadiene to give a stable η⁴-complex [(η⁴-C₅H₆)(η⁵-C₁₇H₁₀Me)Mo(CO)₂][BF₄] that was successfully oxidized to the Mo(IV) dicationic compound [(η⁵-C₅H₅)(η⁵-C₁₇H₁₀Me)Mo(CO)₂][Br][BF₄].     

Synthesis and Characterization of donor‐functionalized ansa‐Cyclopentadienyl‐Indenyl and ansa‐Indenyl‐Indenyl Complexes of Yttrium,Samarium, Thulium,and Lutetium

The stepwise reaction of Me₂SiCl₂ with K[C₅H₃ ^tBuMe‐3] or Li[C₉H₇] and then with K[C₉H₆CH₂CH₂‐ NMe₂‐1] followed by double deprotonation with NaH or LiBu, yields the two dimethylsilicon bridged cyclopentadienyl‐indenyl and indenyl‐indenyl donor‐functionalized ligand systems K₂[(C₅H₂ ^tBu‐3‐Me‐5)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)] ( 1 ), and Li₂[(1‐C₉H₆)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)] ( 2 ), respectively. Treatment of 1 with YCl₃(THF)₃, SmCl₃(THF)_1.77, TmI₃(DME)₃, and LuCl₃(THF)₃ gives the mixed ansa‐metallocenes [(C₅H₂ ^tBu‐3‐Me‐5)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)]LnX (X = Cl, Ln = Y ( 3 ), Sm ( 4 ), Lu ( 5 ); X = I, Ln = Tm ( 6 )), respectively. The reaction of 2 with LuCl₃(THF)₃ yields [(1‐C₉H₆)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)]LuCl ( 7 ). Compound 4 reacts with LiMe to give the corresponding alkyl derivative [(C₅H₂ ^tBu‐3‐Me‐5)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)]Sm(CH₃) ( 8 ). The new complexes were characterized by elemental analyses, MS spectrometry, and NMR spectroscopy. The molecular structures of 5 and 6 were determined by single crystal X‐ray diffraction.     

Synthesis of cationic indenyl- and fluorenyl-arene complexes of ruthenium

Interaction of [Ru(-C ₆ H ₆ )Cl ₂ ] ₂ with indenyl- or fluorenyllithium in THF gives, together with cationic benzene complexes [Ru( ⁵ -C ₉ H ₇ )(-C ₆ H ₆ )]⁺ and [Ru( ⁵ -C ₁₃ H ₉ )(-C ₆ H ₆ )]⁺, the neutral cyclohexadienyl derivatives Ru( ⁵ -C ₉ H ₆ -C ₉ H ₇ ) and Ru( ⁵ -C ₁₃ H ₉ )( ⁵ -C ₆ H ₆ -C ₁₃ H ₉ ), respectively. Interaction of the cyclohexadienyl complexes with Al ₂ O ₃ , Ph ₃ C⁺, and CF ₃ CO ₂ H has been studied. Reaction of Ru( ⁵ -C ₁₃ H ₉ )( ⁵ -C ₆ H ₇ ) with CF ₃ CO ₂ H in the presence of an arene yields cationic cyclohexadienylarene complexes: [Ru( ⁵ -C ₁₃ H ₉ )( ⁶ -arene)]⁺ (arene=C ₆ H ₆ or 1,3,5-Me ₃ C ₆ H ₃ ).A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 699–706, March, 1992.     

New indenyl phosphinooxazoline complexes of iron and their catalytic activity in the Mukaiyama aldol reaction

New phosphinooxazoline (PHOX) η⁵-indenyl complexes of iron were synthesized and applied as catalysts in the Mukaiyama aldol reaction. Reaction of three different PHOX ligands with [Fe(η⁵-Ind)I(CO)₂] afforded the iodide salts of three complexes of the general formula [Fe(η⁵-Ind)(CO)(PHOX)]⁺ in 73-81% isolated yields. The molecular structure of one of the new complexes was determined, revealing a pseudo octahedral coordination geometry about the iron center. The iron complexes are catalytically active in the Mukaiyama aldol reaction between aldehydes and 1-(tert-butyldimethylsilyloxy)-1-methoxyethene to give the corresponding aldol adducts (3 mol % catalyst, 15 min, room temperature, 48-83% isolated yields). A previously synthesized iron complex of the general formula [Fe(η⁵-Cp)(CO)(PHOX)]⁺ was found to be catalytically active in the title reaction as well, but needed three hours at room temperature to convert the starting materials to the products.     

Homolysis of the Ln-N bond: Synthesis, characterization and catalytic activity of organolanthanide(II) complexes with furfuryl- and tetrahydrofurfuryl-functionalized indenyl ligands

A series of new organolanthanide(II) complexes with furfuryl- and tetrahydrofurfuryl-functionalized indenyl ligands were synthesized via one-electron reductive elimination reaction. Treatments of [(Me₃Si)₂N]₃Ln^III(μ-Cl)Li(THF)₃ (Ln = Yb, Eu) with 2 equiv. of C₄H₇OCH₂C₉H₇ (1) or C₄H₃OCH₂C₉H₇ (2), respectively in toluene at moderate high temperatures produced, after workup, the corresponding organolanthanide(II) complexes with formula [η⁵:η¹-(C₄H₇OCH₂C₉H₆)]₂Ln^II (Ln = Yb (5), Ln = Eu (6)) and [η⁵:η¹-(C₄H₃OCH₂C₉H₆)]₂Ln^II (Ln = Yb (7), Ln = Eu (8)) in reasonable to good yields. Treatments of [(Me₃Si)₂N]₃Ln^III(μ-Cl)Li(THF)₃ (Ln = Yb, Eu) with 2 equiv. of C₄H₇OCH₂C₉H₆SiMe₃ (3) or C₄H₃OCH₂C₉H₆SiMe₃ (4), respectively, in toluene at moderate high temperatures afforded, after workup, the corresponding organolanthanide(II) complexes with formula [η⁵:η¹-(C₄H₇OCH₂C₉H₅SiMe₃)]₂Ln^II (Ln = Yb (9), Ln = Eu (10)) and[η⁵:η¹-(C₄H₃OCH₂C₉H₅SiMe₃)]₂Ln^II (Ln = Yb (11), Ln = Eu (12)) in good to high yields. All the compounds were fully characterized by spectroscopic methods and elemental analyses. The structure of complex 9 was additionally determined by single-crystal X-ray analyses. Studies on the catalytic activities of complexes showed that the complexes having silyl group functionalized indenyl ligands have high catalytic activities on ε-caprolactone polymerization. The temperatures, substituted groups on the indenyl ligands of the complexes, and solvents effects on the catalytic activities of the complexes were examined.     

Synthesis and structural characterization of unsymmetrical osmocenes containing the pentamethylcyclopentadienyl ligand

Treatment of dibromo(pentamethylcyclopentadienyl)osmium(III) dimer with alkali metal salts of a variety of cyclopentadienyl derivatives provides a simple approach to the synthesis of unsymmetrical osmocenes containing the pentamethylcyclopentadienyl ligand. Furthermore, the reaction of dibromo(pentamethylcyclopentadienyl)osmium(III) with alkali metal salts of pyrrole and 3,5-di-tert-butylpyrazole afforded the corresponding pentamethylcyclopentadienylosmium complexes containing η⁵-pyrrolyl or η⁵-3,5-di-tert-butylpyrazolato ligands. This overall synthetic approach afforded pentamethylosmocene (64%), (η⁵-pentamethylcyclopentadienyl)(η⁵-indenyl)osmium (36%), (η⁵-pentamethylcyclopentadienyl)(η⁵-fluorenyl)osmium (30%), (η⁵-pyrrolyl)(η⁵-pentamethylyclopentadienyl)osmium (30%), and (η⁵-3,5-di-tert-butylpyrazolato)(η⁵-pentamethylcyclopentadienyl)osmium (38%). The new complexes were characterized by spectroscopic and analytical techniques, and by single crystal X-ray structural determinations. In the solid state, all of the new complexes exist as eclipsed metallocenes.     

利用二维核磁共振方法研究取代茚基金属钛、锆配合物 的空间结构

通过^1H-^1HTOCSY和^1H-^1HNOESY谱对一系列新型结构的取代茚基钛、锆配合物进行了结构上的解析，并由此发现夹心结构的锆配合物中，两个茚环(或茚环和茂环)以及茚环上的取代基之间存在核的Overhauser效应，这对于茚环相对空间结构的判断提供了有效的证据。     

Synthesis and structural characterization of ferrocenyl indenyl derivatives

In this study, four ferrocenyl indenyl derivatives, C₉H₇–C≡C–Fc (1), C₉H₇–C≡C–Ph–Fc (2), C₉H₇–C≡C–Ph–C≡C–Fc (3), and C₉H₇–Ph–C≡C–Fc (4) (where C₉H₇=indenyl; Fc=C₅H₅FeC₅H₄; Ph=C₆H₅), have been synthesized by Sonogashira and Suzuki cross-coupling reactions and characterized by elemental analysis, and FT-IR, ¹H, ¹³C-NMR, and MS spectroscopic methods, respectively. The molecular structures of 1, 2, and 4 were determined by X-ray single crystal diffraction. Two molecules appeared in the crystal structure of 4, and they interact through an intermolecular hydrogen bond. The electrochemical redox potential differences in 1–4 were investigated using cyclic voltammetry and calculations.     

Syntheses and characterization of η-cyclopentadienyl and η-indenyl ruthenium(II) complexes of arylazoimidazoles: The molecular structure of the complex [(η-C5H5)Ru(PPh3)(C6H5-NN-C3H3N2)]

The complex [(η⁵-C₅H₅)Ru(PPh₃)₂Cl] (1) reacts with several arylazoimidazole (RaaiR′) ligands, viz., 2-(phenylazo)imidazole (Phai-H), 1-methyl-2-(phenylazo)imidazole (Phai-Me), 1-ethyl-2-(phenylazo)imidazole (Phai-Et), 2-(tolylazo)imidazole (Tai-H), 1-methyl-2-(tolylazo)imidazole (Tai-Me) and 1-ethyl-2-(tolylazo)imidazole (Tai-Et), gave complexes of the type [(η⁵-C₅H₅)Ru(PPh₃)(RaaiR′)]⁺ {where R, R′ = H (2), R = H, R′ = CH₃ (3), R = H, R′ = C₂H₅ (4), R = CH₃, R′ = H (5), R, R′ = CH₃ (6), R = CH₃, R′ = C₂H₅ (7)}. The complex [(η⁵-C₉H₇)Ru(PPh₃)₂(CH₃CN)]⁺ (8) undergoes reactions with a series of N,N-donor azo ligands in methanol yielding complexes of the type [(η⁵-C₉H₇) Ru(PPh₃)(RaaiR′)]⁺ {where R, R′ = H (9), R = H, R′ = CH₃ (10), R = CH₃, R′ = H (11), R = CH₃, R′ = C₂H₅ (12)}, respectively. These complexes were characterized by FT IR and FT NMR spectroscopy as well as by analytical data. The molecular structure of the complex [(η⁵-C₅H₅)Ru(PPh₃)(C₆H₅-NN-C₃H₃N₂)]⁺ (2) was established by single crystal X-ray diffraction study.     

Synthesis of molybdenocene(IV) and tungstenocene(IV) tropolonato complexes: Its derivative containing calix[4]arene moiety

The cationic di-μ-hydroxo dinuclear complexes of molybdenocene and tungstenocene [Cp₂M(μ-OH)₂MCp₂]⁺ (Cp = η-C₅H₅; M = Mo or W) react with tropolone to afford corresponding tropolonato complexes [Cp₂M(trop)]⁺ (trop = C₇H₅O₂). The products were investigated by IR, ¹H NMR, and ¹³C NMR spectroscopy as well as by X-ray crystallography (M = W). The structure shows that the central metal is surrounded by a distorted tetrahedral array of the two centers of cyclopentadienyl ligands and the two oxygen atoms of tropolonato ligand. The reaction has been extended to the synthesis of calix[4]arene receptor functionalized at the 1,3-positions of the upper rim with two tropolonato-molybdenocene centers.     

Synthesis, characterization and reactivity of tetramethylphospholyl complexes of scandium

Reaction of 2 equiv. of (C₄Me₄P)Li(tmeda) (tmeda = tetraethylenediamine) with 1 equiv. of ScCl₃(THF)₃ gave the new compound (η⁵-C₄Me₄P)₂ScCl₂Li(tmeda) (1), which was characterized by X-ray crystallography. A phospholyl moiety in 1 is labile, as demonstrated by reactions of 1 with LiCH(SiMe₃)₂ and Cp^∗Li (Cp^∗ = C₅Me₅) to afford, respectively, (η⁵-Me₄C₄P)Sc[CH(SiMe₃)₂]Cl₂Li(tmeda) (4) and (η⁵-Me₄C₄P)Cp^∗ScCl₂Li(tmeda) (5). Attempts to generate alkyl derivatives of the general type (η⁵-C₄Me₄P)₂ScR (R = alkyl) were unsuccessful.