EXAFS and FTIR structural characterization for the crystal of monomeric tetraphenylporphyrinato gadolinium:[Gd(TPP)acac 8H_2O.3TCB]

The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.     

Unexpected Synthesis and Crystal Structure of Macrocyclic Nickel Complex Involving Rare S-Cl Bond

A novel complex of [NiL(OOCNH2C2H3SClO3)]·H2O was obtained unexpectedly by the reaction of [Ni(rac-L)](ClO4)2 with l-cysteine (L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra- azacyclotetradecane), and characterized by EA, IR, ESI-MS and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group P212121 with a=9.211(12), b=14.942(19), c=19.002(2), Mr=563.80, V=2615.3(6)3 , Z=4, Dc=1.432 g/cm3 , F(000)=1204, μ=0.966 mm-1 , the final R=0.0565 and wR=0.1515. The central nickel(Ⅱ) ion displays a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L, and one oxygen and one nitrogen atoms of l-cysteine. The sulfur atom of l-cysteine instead of oxygen atom links directly with the chlorine atom of perchlorate. The title complex is the first example of perchlorate salt involving the sulfur atom.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF A NOVEL TETRANUCLEAR COPPER (Ⅰ) CLUSTER COMPLEX, Cu_4(α-C_(10)H_7CSS_2)_4·1/2CS_2

The title compound has been synthesized by the reaction of sodium α-dithionaphthoatewith CuCl_2 in an alkaline aqueous solution or by the reaction of α-dithionaphthoic acid withCuCl_2 in an organic solvent, The crude product was recrystallized in a mixture of CS_2 andC_2H_5OH. The crystals obtained are red and stable in air. The structure of the title compound is determined by a single-crystal X-ray diffractionanalysis. The crystal belongs to monoclinic space group C_(2h)~5- P(2_1/a) with unit cell parameters:a= 16.453(3)A, b=12.651(4)A, c=23.182(7)A, β=100.5(2)°, V=4744.6A~3,Z=4. Thestructure was refined to R=0.06 for 4707 reflections. In the molecule, Cu_4 cluster has a distorted tetrahedral configuration. Surrounding thistetrahydron are four α-perthionaphthoate ligands, coordinated to copper through the sulfuratoms. One of the sulfur atoms in each ligand forms sulfur bridge with copper atoms,while the other is coordinated to only one copper. The three Cu--S bonds formed by thethree sulfur atoms with a given copper atom are approximately coplanar. Each group--C--S_2 with Cu atom on a vertex of the tetetrahedron forms a five-member ring. Thesefive-member rings are also approximately cooplanar. The molecule possesses an approachingS_4 point symmetry. The mechanism for the formation of the title compound involves a redox reaction.which is discussed in this paper.     

Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand

Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [(HOC6H2R2-4,6)(CH2)SC(B10H10) C(Ph)2P=S, R=tBu] was synthesized by the reaction of CpZrCl3(Cp=η5-C5H5) with sodium salt of ligand 2. Zirconium complex 3 was characterized by elemental and NMR analyses. DFT calculations were also performed on complex 3 to analyze the stereochemistry. The results from DFT calculations indicate that structure S1, in which no sulfur atom bonds to the zirconium atom, exists at the lowest energy level. In the presence of methylaluminoxane(MAO), complex 3 exhibited good catalytic activities for ethylene polymerization and long life-time up to 10 h. Moreover, the complex 3/MAO system displayed excellent catalytic activities toword ethylene copolymerization with 1-hexene or polar olefins.     

Synthesis and Crystal Structure of a Novel 3D Inorganic-organic Hybrid Metallic Coordination Polymer, [Na2Cd（2,6-pyda）（N3）2（H2O）6]n

A novel coordination polymer [Na2Cd（2,6-pyda）（N3）2（H2O）6]n （2,6-H2pyda = 2,6- pyridinedicarboxylic acid） has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c, with a = 24.416（4）, b = 10.7638（17）, c = 6.9224（11） A^°, β= 106.124（2）A^°, V = 1747.7（5） A^°3, Mr = 515.64, De= 1.960 g/cm^3,μ = 1.365 mm^-1, F（000） = 1024, Z = 4, the final R = 0.0426 and wR = 0.1320. In the title complex, there exist two kinds of metal centers in the structure, cadmium ions and sodium ions. The Cd（Ⅱ） atom shows a distorted pentagonal-dipyramidal geometry defined by two O and one N atoms from one deprotonated pyda ligand and four N atoms from four μ-1,1,3 azido groups. The adjacent cadmium atoms are bridged via two μ-1,1,3 azido groups, along the c axis to afford an extended chain. There is also a 2D network which is comprised of binuclear subunits [NaE（H2O）6] connected by O atoms from coordinated water between the adjacent Cdn（pyda）n（Na）2n infinite chains. Furthermore, each cadmium atom is connected with four adjacent sodium atoms through the bridging N3- ligand in μ-1,3 patterns. Thus, the title complex exhibits a novel three-dimensional network structure.     

Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.     

Synthesis and Structure Study of Molybdenum Complex Mo[o-NHCOCH_3-m-NO_2C_6H_3COOH]_2_O2Cl_2·PhCl

The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3) A .b= 19. 544 (4 ) A . c = 14. 091 (6) A .β=94.06(3)°,V'=3080.3 A3 and Z=4. The structure was refined to R=0. 061.The coordination number for the Mo atom Is six. The coordination polyhedron formed by four O atoms and two Cl atoms around the Mo atom is a distorted octahedron. Four O atoms and one Mo atom construct a plane. Two benzyl planes in coordinate groups and the benzyl plane of solvent are almost parallel. The quantum-chemical calculations were carried out. There are hydrogen bonds in the Complex. The EHMO calculations and the existence of hydrogen bonds prove that the O atoms are stronger coordinated atoms in the carbonyls than in the carboxyls.     

SYNTHESIS AND STRUCTURE OF Ni_2(PBu_3~n)_2(SC_7H_6S)_2

<正> The nickel(Ⅱ) complex Ni2(PBu3n)2(tdt)2(tdt = SC7H6S2-) containing dithiolato and phosphino ligands has been prepared and characterized by X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a = 14. 423(4), b = 15. 053(3), c=10. 648(3)(?), α=93.,95(2), β=100. 31(3), γ = 84. 16(2)°; V =2259.6 (?)3; Z = 2, Dc= 1. 22 gem-3, Mr = 830. 57; μ = 11. 076cm-1, F (000) = 888. In the complex, the Nickel atoms are linked by two bridging sulfur atoms from the two tdt ligands with the Ni-Ni distance of 2. 679 (?) . and each nickel atom is four coordinated by one phosphorus and three sulfur atoms with a square-planar geometry, the average length of Ni -S bond is 2. 193(?) and that of Ni-P bond 2.186(?).     

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ) and Copper(Ⅱ) Complexes

A new kind of Schiff base HL(HL= 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-Leucine methyl ester) and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2(L′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine) have been synthesized and structurally determined by X-ray diffraction. For HL: crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1: the Ni(Ⅱ) ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2: the Cu(Ⅱ) ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.     

CRYSTAL STRUCTURE OF ORGANOLANTHANIDE [{Li(THF)_2}_2 (μ-Cl)_4(η~5-C_5H_5)Pr(THF)]

<正> The title complex crystallizes in the orthorhombic space group Pna21 with Mr = 570. 8, a = 16. 927(6), b = 18.942(7), c=10. 618(5)(?) and Z = 4. The structure was solved by Patterson and Fourier techniques and refined by block-diagonal least squares techniques to R = 0. 090 and Rw = 0. 093 for 1553 reflections with I>1. 5σ(I). The Pr3+ ion is bonded to five carbon atoms of cyclopentadi-enyl ring, four μ-chlorine atoms and one oxygen atom of THF in an octahedral geometry with the Pr-C distances in the range 2. 6.7 - 2. 79(?)(av. 2. 76(?)) , the Pr-Cl distances in the range 2. 81 - 2. 92(?) (av. 2. 86(?)) and the Pr -O distance of 2. 51 (?). Each Li+ ion is coordinated by two μ-chlorine atoms and two oxygen atoms from THF in a tetrahedral geometry with the Li-Cl distances in the range 2. 24 - 2. 61(?) (av. 2. 43(?)) and the Li -O distances in the range 1. 86-1. 94(?)(av. 1. 91(?)). The Pr atom and the two Li atoms are bridged asymmetrically by the chlorine atoms.     

Synthesis and Structural Characterization of New Zirconium(IV) Bent Metallocenes comprising η8‐Cyclooctatetraenyl and Bulky Cyclopentadienyl Ligands

The new zirconium bent metallocenes (COT)Zr(Cp^tBu2)Cl ( 1 ) and (COT)Zr(Cp′′)Cl ( 2 ) were synthesized in a straightforward manner and in high yields ( 1 : 91 %, 2 : 86 %) by treatment of in situ‐prepared (COT)ZrCl₂(THF) with 1 equiv. of K(Cp^tBu2) or K(Cp′′), respectively (COT = η⁸‐cyclooctatetraenyl; Cp^tBu2 = η⁵‐1,3‐di‐tert‐butylcyclopentadienyl; Cp′′ = η⁵‐1,3‐bis(trimethylsilyl)cyclopentadienyl). Subsequent reaction of 1 with 1 equiv. of phenyllithium afforded the σ‐phenyl derivative (Cp^tBu2)Zr(COT)Ph ( 3 ) as orange crystals in 83 % isolated yield. All three new compounds were structurally characterized through single‐crystal X‐ray diffraction.     

Bis(η5‐isopropyltetramethylcyclo­pentadienyl)(tetrahydroborato‐κ3H,H′,H′′)(tetrahydrofuran‐O)‐samarium(III): a lanthanidocene complex with a tridentate tetrahydroborato ligand

The lanthanidocene complex [Sm(BH₄)(C₁₂H₁₉)₂(C₄H₈O)], (I), shows a distorted tetrahedral arrangement around the central Sm^III atom. It consists of two η⁵‐isopropyltetramethylcyclopentadienyl ligands, one tetrahydroborato (BH₄^?) ligand bridging via H atoms to the lanthanide atom and one coordinating tetrahydrofuran (thf) molecule. The BH₄^? unit of (I) coordinates as a tridentate ligand with three bridging H atoms and one terminal H atom [Sm—B—H4 176 (2)°]. The η⁵‐isopropyl­tetra­methylcyclopentadienyl ligands of this bent‐sandwich complex [Cp1—Sm—Cp2 133.53 (1)° where Cp denotes the centroid of the cyclopentadienyl ring] adopt staggered conformations.     

Synthesis and Characterization of Multiferrocenyl‐Substituted Group 4 Metallocene Complexes

The reaction of different metallocene fragments [Cp₂M] (Cp=η⁵‐cyclopentadienyl, M=Ti, Zr) with diferrocenylacetylene and 1,4‐diferrocenylbuta‐1,3‐diyne is described. The titanocene complexes form the highly strained three‐ and five‐membered ring systems [Cp₂Ti(η²‐FcC₂Fc)] ( 1 ) and [Cp₂Ti(η⁴‐FcC₄Fc)] ( 2 ) (Fc=[Fe(η⁵‐C₅H₄)(η⁵‐C₅H₅)]) by addition of the appropriate alkyne or diyne to Cp₂Ti. Zirconocene precursors react with diferrocenyl‐ and ferrocenylphenylacetylene under C? C bond coupling to yield the metallacyclopentadienes [Cp₂Zr(C₄Fc₄)] ( 3 ) and [Cp₂Zr(C₄Fc₂Ph₂)] ( 5 ), respectively. The exchange of the zirconocene unit in 3 by hydrogen atoms opens the route to the super‐crowded ferrocenyl‐substituted compound tetraferrocenylbutadiene ( 4 ). On the other hand, the reaction of 1,4‐diferrocenylbuta‐1,3‐diyne with zirconocene complexes afforded a cleavage of the central C? C bond, and thus, dinuclear [{Cp₂Zr(μ‐η¹:η²‐C?CFc)}₂] ( 6 ) that consists of two zirconocene acetylide groups was formed. Most of the complexes were characterized by single‐crystal X‐ray crystallography, showing attractive multinuclear molecules. The redox properties of 3 , 5 , and 6 were studied by cyclic voltammetry. Upon oxidation to 3 ⁿ⁺, 5 ⁿ⁺, and 6 ⁿ⁺ (n=1–3), decomposition occured with in situ formation of new species. The follow‐up products from 3 and 5 possess two or four reversible redox events pointing to butadiene‐based molecules. However, the dinuclear complex 6 afforded ethynylferrocene under the measurement conditions.     

Synthese und Charakterisierung von Metallocen-Chelaten heterocyclischer 1,2-Diselenolate

Synthesis and Characterization of Metallocene Chelates of Heterocyclic 1,2-Diselenolates Synthesis and properties of metallocen diselenolates Cp₂^RML (Cp^R = η⁵-C₅H₄CH₃ (Cp′); η⁵-C₅(CH₃)₄ C₂H₅ (Cp^o)) of titanium(IV) and vanadium(IV) with L = dsit (1,3-dithiole-2-thione-4,5-diselenolate), dsise (1,3-dithiole-2-selone-4,5-diselenolate) dsitse (1,3-thiaselenole-2-selone-4,5-diselenolate) and dsis (1,3-diselenole-2-selone-4,5-diselenolate) are described. The structures of these compounds in solution are discussed using ¹H, ¹³C, ⁷⁷Se NMR and EPR data. Their voltammetric behaviour is investigated in dichloromethane. The activation parameters of the chelate ring inversion of the titanocene diselenolates (Cp₂^RTiL) and the x-ray structures of Cp₂′Ti(dsit), Cp₂^oTi(dsit); Cp₂^oTi(dsise) (2 modifications) and Cp₂^oTi(dsis) are reported.     

(Tetra­hydro­furan)­potassium mer‐trans‐tris­(carbazolyl)­di­chloro(tetra­hydro­furan)­zirconate

In the title compound, [K(C₄H₈O)][ZrCl₂(C₁₂H₈N)₃(C₄H₈O)], the Zr atom is pseudo‐octahedral, with two Cl ligands in trans positions. There is extensive interaction between the potassium cation and two of the aromatic carbazolyl ligands in η⁶ [C⃛K = 3.167 (3)–3.331 (3) Å] and η² [C⃛K = 3.147 (3)–3.268 (2) Å] fashions.     

Sekundäre Hydroxyalkylphosphane: Synthese und Charakterisierung mono‐, bis‐ und trisalkoxyphosphan‐substituierter Zirconiumkomplexe und des heterobimetallischen Dreikernkomplexes [Cp2Zr{O(CH2)3PHMes(AuCl)}2]

Secondary Hydroxyalkylphosphanes: Synthesis and Characterization of Mono‐, Bis‐ and Trisalkoxyphosphane‐substituted Zirconium Complexes and the Heterobimetallic Trinuclear Complex [Cp₂Zr{O(CH₂)₃PHMes(AuCl)}₂] The secondary hydroxyalkylphosphanes RPHCH₂OH [R = 2,4,6‐Me₃C₆H₂ (Mes) ( 1 ), 2,4,6‐ⁱPr₃C₆H₂ (Tipp) ( 2 )], 1‐AdPH‐2‐OH‐cyclo‐C₆H₁₀ ( 3 ) and RPH(CH₂)₃OH [R = Ph ( 4 ), Mes ( 5 ), Tipp ( 6 ), Cy ( 7 ), ^tBu ( 8 )] were obtained from primary phosphanes RPH₂ and formaldehyde ( 1 , 2 ) or from LiPHR and cyclohexene oxide ( 3 ) or trimethylene oxide ( 4 ‐ 8 ). Starting from 5 or 7 and [Cp^R₂ZrMe₂] [Cp^R = C₅EtMe₄ (Cp°), C₅H₅ (Cp), C₅MeH₄ (Cp′)], the monoalkoxyphosphane‐substituted zirconocene complexes [Cp^R₂Zr(Me){O(CH₂)₃PHMes}] [Cp^R = Cp° ( 9 ), Cp ( 10 )] were prepared. With [Cp^R₂ZrCl₂], the bisalkoxyphosphane‐substituted complexes [Cp′₂Zr{O(CH₂)₃PHMes}₂] ( 11 ) and [Cp₂Zr{O(CH₂)₃PHCy}₂] ( 12 ) are obtained, and with [Tp^RZrCl₃], the trisalkoxyphosphane‐substituted zirconium complexes [Tp^RZr{O(CH₂)₃PHMes}₃] [Tp^R = trispyrazolylborato (Tp) ( 13 ), Tp^R = tris(3,5‐dimethyl)pyrazolylborato (Tp*) ( 14 )] are prepared. The reaction of 5 with [AuCl(tht)] (tht = tetrahydrothiophene) yielded the mononuclear complex [AuCl{PHMes(CH₂)₃OH}] ( 15 ). The trinuclear complex [Cp₂Zr{O(CH₂)₃PHMes(AuCl)}₂] ( 16 ) was obtained from [Cp₂ZrCl₂] and 15 . Compounds 1 ‐ 16 were characterized spectroscopically (¹H‐, ³¹P‐, ¹³C‐NMR; IR; MS) and compound 2 also by crystal structure determination. The bis‐ and trisalkoxyphosphane‐substituted complexes 11‐14 and 16 were obtained as mixtures of two diastereomers which could not be separated.     

ansa‐[(tert‐Butylamino)(isodicyclo­pentadienyl)dimethylsilane]Zr(NMe2)2 prepared by an amine‐elimination reaction

An amine‐elimination reaction was used to obtain the title compound, i.e. (N‐tert‐butyl‐N‐{[(1,2,3,3a,7a‐η)‐4,5,6,7‐tetra­hydro‐4,7‐methano‐1H‐inden‐2‐yl]­di­methyl­silyl}amido‐κN)bis(N‐methyl­methanaminato‐κN)­zirconium(IV) or [isodiCpSiMe₂N‐tert‐butyl]Zr(NMe₂)₂ (Cp is cyclo­penta­dienyl), [Zr(C₁₆H₂₅NSi)(C₂H₆N)₂], in very good yield. Treatment of isodiCpHSiMe₂NH‐tert‐butyl with Zr(NMe₂)₄ leads to the formation of a yellow solid that can be purified by sublimation. The single‐crystal structure of the product shows the exo complexation of the isodi­cyclo­penta­dienyl ligand to the Zr atom. The Cp portion of this ligand is bonded to the Zr atom in a η⁵ manner, with a Zr—Cg (Cg is the ring centroid) distance of 2.2352 (10) Å. The isodiCpSiMe₂N‐tert‐butyl ligand has a constrained geometry, which is exhibited by the small angle of 95.55 (10)° for N—Si—C_Cp.     

Reaction of Cp2ZrCl2 with Inorganic Amides

The reactions of [η⁵‐Cp₂ZrCl₂] (Cp = η⁵‐C₅H₅) with [K(THF)_n][N(PPh₂)₂] (n = 1.25—1.5) and K[CH(PPh₂NSiMe₃)₂] are reported. The first reaction led to the monoamido complex [η⁵‐Cp₂Zr(Cl)N(PPh₂)₂] in which the {(Ph₂P)₂N}^— ligand — via a phosphorous and the nitrogen atom — is coordinated to the zirconium atom in a chelating (η²) fashion. Reaction of the potassium methanide compound, K{CH(PPh₂NSiMe₃)₂} with zirconocene dichloride yield the carbene‐like mono cyclopentadienyl complex [η⁵‐CpZr(Cl){C(PPh₂NSiMe₃)₂}]. The complex is formed by a salt metathesis and concomitant a cyclopentadiene extrusion.     

Synthese und Molekülstruktur von meso-(1,2,3-Tricyclohexyltriphosphan-1,3-diyl)zirkonocen(IV), Cp2 (Cp = η5−C5H5, Cy = C6H11)

Synthesis and Crystal Structure of meso-(1,2,3-Tricyclohexyltriphosphane-1,3-diyl)zirconocene(IV), Cp₂ (Cp = η⁵?C₅H₅, Cy = C₆H₁₁) Cp₂ZrCl₂ reacts with Li(THF)₂PHCy (Cy = C₆H₁₁) to yield the metallacyclic compound Cp₂ 1. , The ³¹P{¹H} NMR spectrum of 1 , shows a coupling pattern for an A₂X system, indicating the presence of only the meso-forms in solution, which are also present in the solid state. 1 , crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 12.984(8), b = 9.241(7), c = 23.05(1) Å, β = 93.48(4)°, V = 2760.1 ų and four formula units in the unit cell (2718 independent observed reflections, R = 7.3%). The central ZrP₃ ring in 1 , is almost planar. The Zr? P bond lengths of 2.618(4) and 2.628(4) Å are nearly identical.     

A doubly bridged isodicyclopentadienyl zirconium complex: bis{N‐(3,5‐dimethylphenyl)‐N‐[(η5‐isodicyclopentadien‐2‐yl)dimethylsilyl]amido‐κN}zirconium(II) diethyl ether solvate

Transmetallation of the dilithium salt of (3,5‐dimethyphenyl­amino)(isodicyclopentadienyl)dimethylsilane by treatment with zirconium tetrachloride in a 2:1 ratio leads to the substitution of all four chloride ligands. With the applied stoichiometry, the title complex, [Zr(C₂₀H₂₅NSi)₂]·C₄H₁₀O, was obtained and crystallized from diethyl ether. X‐ray diffraction characterization showed that both isodi­cyclo­penta­dienyl ligands (alternatively called 4,5,6,7‐tetrahydro‐4,7‐methano‐1H‐indene) are complexed to the metal on their exo face in a completely stereoselective manner and that they are η⁵‐bonded to the Zr atom.