Zur Bildung und Stabilität von Difluormethylenphosphoranen,R3P⊕-C̄–F2

Inhaltsübersicht. Die Reaktion von Difluorhalogenmethanen, CF₂X₂, mit Phosphanen, R₃P, in Gegenwart von Metallen und Carbonylverbindungen, R″R′CO, führt zur Bildung geminaler Difluorolefine, R″R′C=CF₂. Die sorgfältige Untersuchung der Einzelschritte dieser komplexen Reaktion zeigt, daß intermediär Difluorhalogenmethylphosphoniumhalogenide, [R₃P–CF₂X]X, und Difluormethylenphosphorane, R₃P^⊕ – c?^?-F₂, gebildet werden. Die Phosphoniumsalze sind stabil und können als kristalline Substanzen isoliert werden. Durch Metalle oder Phosphene werden sie zu den instabilen Difluormethylenphosphoranen reduziert. Diese zersetzen sich beim Fehlen geeigneter Reaktionspartner in Phosphan und Difluorcarben, CF₂. Ihre Bildung durch Addition von CF₂ an R₃P ist nicht möglich. Mit Halogenwasserstoffen bilden sie Difluormethylphosphoniumsalze, [R₃P-CHF₂]X. Formation and Stability of Difluoromcthylene Phosphoranes, R₃P^⊕ —c?F₂ In the presence of metals and carbonyl compounds, R″R′CO, the reaction of difluoro-halomethanes, CF₂X₂, with phosphanes, R₃P, leads to the formation of geminal difluoroolefins, R″R′C=CF₂. Our investigations have proved that difluorohalomethylphosphonium halides, [R₃P–CF₂X]X, and difluoromethylene phosphoranes, R₃P^⊕–C??F₂, are formed intermediately. The phosphonium salts are stable. They can be isolated as crystalline substances. They are reduced by metals or phosphanes forming unstable difluoromethylene phosphoranes as intermediates. These decompose into phosphane and difluorocarbene, CF₂, if suitable reactants are absent. Their reaction with hydrogen halides, HX, yields difluoromethylphosphonium salts, [R₃P–CHF₂]X. The formation of difluoromethylene phosphoranes by addition of CF₂ to R₃P is not possible.     

Phosphoniumsalze mit Hydrogendihalogenidanionen HCl2−, HBr2− Hl2− oder HBrCl−

Phosphonium Salts with Hydrogen Dihalide Anions HCl₂^?, HBr₂^?, HI₂^?, or HBrCl^? Phosphonium hydrogen dihalides [R₃PR′][XHY] (X = Y = Cl, Br, I; X = Br, Y = Cl) resp. [R₃PH]HBr₂ are obtained as extremely hydrolyzable crystals by reaction of phosphonium halides or tertiary phosphanes with hydrogen halide. According to IR spectroscopic results the solid compounds mostly contain anions [XHX]^? with symmetric hydrogen bonds. In solution ¹H NMR measurements show a slight (X = Cl, Br) or considerable (X = I) dissociation according to HX₂^? ? X^? + HX. On heating the solid compounds decompose with formation of hydrogen halide and [R₃PR′]X or [R₃PH]X. In this process the hydrogen bromidechlorides [R₃PR′][BrHCl] exclusively eliminate HCl. NMR studies (¹H und ³¹P) with solutions containing [R₃PH]HBr₂ (R = phenyl, 1-naphtyl) or HBr and Ph₃P in varying molar ratios show that a fast proton exchange between the competing Lewis bases R₃P and Br^? exists.     

Zur Reaktion von Halomethylphosphoniumhalogeniden, [R3PCYnX3–n]X,mit Phosphanen,R′3P

On the Reaction of Halomethylphosphonium Halides, [R₃PCY_nX_3–n]X, with Phosphanes, R′₃P The results of the reaction of 19 different halomethylphosphonium halides, [R₃PCY_nX_3–n]X (R = Ph, n-Bu, Me₂N, Et₂N; Y = H, F; X = Cl, Br, I; n = 0–2), with Ph₃P, n-Bu₃P, and (R₂N)₃P are presented. As reaction products bisphosphonium salts, [R₃P? CY_nX_2–n? PR′₃]X₂, and phosphoranylphosphonium salts, [R₃P=CY? PR′₃]X, or reduced (halo)methyl-phosphonium salts, [R₃PCHY_nX_2–n]X, are obtained. [Ph₃PCBrF₂]Br and [Bu₃PCBrF₂]Br react with R′₃P by trans-alkylation forming [R′₃PCBrF₂]Br. The factors influencing the course of the reaction are discussed.     

Displacement of dienes from planar complexes Reaction of (1,2-bisdiphenylphosphinoethane)(3a,4,7,7a-tetrahydro-exo-6-methoxy-endo-4,7-methanoindene-endo-5τ,2π)-palladium(II) and -platinum(II) cations with acids

A kinetic study of the reaction of [M(C₁₀H₁₂ · OCH₃)(P)]⁺ complexes (M = Pd, Pt; PP = 1,2-bisdiphenylphosphinoethane; C₁₀H₁₂ = endo-dicyclopentadiene) with hydrogen halides, HX (X = Cl, Br) in aqueous methanol at 35° C is described. The proposed mechanism involves slow formation of the solvato species [M(C₁₀H₁₂)(solv.)(P)]²⁺ followed by fast reaction with X^- to give M(PP)X₂.     

Methandiphosphor-Halogen-Verbindungen

Methylene-diphosphorus Halides The synthesis of methylene-bridged diphosphorus halides of the type X₂P(Z)CH₂PX₂, X₂P(Z)CH₂P(Z)X₂ and F₄PCH₂P(Z)X₂(with X = F, Cl; Z = O, S) as well as the preparation of the fluorophosphorane F₄PCH₂PF₄, and of the two anions, [F₅PCH₂PF₅]^2? and [F₅PCH₂P(O)F₂]^?, is reported.     

Fluoridolyse von N-Phosphorylphosphazenen

Fluoridolysis of N-Phosphoryl Phosphazenes In the reaction of the N-phosphoryl phosphazenes X₃P?N? P(Y)X₂ (X = Cl, PhO, Et₂N, CF₃CH₂O, PrS, Ph; Y = O, S) ( 1 – 18 ) with Et₃N · nHF (n ≈? 3 or 0.6) fluoro derivatives of N-phosphoryl phosphazenes (see table 2) as well as N-phosphorylated imiddotetrafluorophosphates, [F₄P?N? P(Y)Cl₂]^? (Y = O, S), and imidopentafluorophosphates, [F₅P? N? P(Y)X₂]^2? or [F₅P? NH? P(O)X₂]^? (see table 3), are formed. t-BuNHPCl₂?N? POCl₂ reacts in acetonitrile with Et₃N or i-Pr₂EtN to form a product, representing probably the diazadiphosphetine ( 5 b ).     

Structural and Thermodynamic Characteristics of Compounds X2MYH2 (M = Al,Ga, In; X = F,Cl, Br,I; Y = N,P, As) Formed by Hydrogen Halide Elimination from Donor-Acceptor Complexes X3MYH3

Geometry and thermodynamic characteristics of complexes X₂MYH₂ (M = Al, Ga, In; X = F, Cl, Br, I; Y = N, P, As) and their components were found by the B3LYP density functional method with the LANL2DZ(d,p) basic set. The nitrogen complexes X2MNH2 have a planar structure, whereas the phosphorus and arsenic complexes are pyramidal. Upon HX elimination, the dissociation energy of the M-Y bonds considerably increases (by 150-270 kJ mol^{- 1}), which makes the dissociation of X2MYH2 into components thermodynamically unfeasible even at temperatures about 1000°C. A linear correlation between the dissociation enthalpies of M-Y bonds in the X₃MYH₃ and X₂MYH₂ complexes was found for each central atom M, which makes it possible to estimate the dissociation enthalpies of coordination-unsaturated compounds of the Group IIIa elements from the dissociation enthalpies of their coordination-saturated analogs. The enthalpies of dimerization of X₂MYH₂ fall in the range from 40 (Y = P, As) to 260 kJ mol^{- 1} (Y = N), which makes the process X₃MNH₃ = [X₂MNH₂]₂ + HX with the retention of the metal-nitrogen bond more favorable than the dissociation of the initial complex into the components. Thus, dimers [X₂MNH₂]₂ can be intermediates in chemical deposition of nitrides from the gas phase of donor-acceptor complexes.     

Rhenium,part XIV. Studies on the action of hydrogen halides on [ReO2en2]+

Summary The products from the reaction oftrans-dioxobis(ethylenediamine)rhenium(V) halides with hydrogen halides have been investigated. Dilute (2M) and concentrated hydrochloric acid react with (ReO₂en₂)Cl in the cold to give ReO(OH)enCl₂ and IRe(OH)₂enCl₂]Cl respectively, while with hot 6M HCl [ReOCl₅]^2– is formed. Dilute solutions of HX protonate [ReO₂en₂]X (X = Br and I) giving [ReO(OH)en₂]X₂ which are converted slowly into ReO(OH)enBr₂ and [ReO(OH)en2](I₃)₂. Hot and concentrated solutions of HX reduce Re^v in (ReO₂en2 )X (X = Br and I) giving enH₂(ReBr₆) and ReI₄en. The thermal decomposition of (ReO₂en₂)X (X = Cl, Br and I) has been studied by thermogravimetry and a polymeric compound, Re₂O₇en₂, has been isolated by heating (ReO₂en₂)X at 200°. The compounds have been characterised by molecular conductivities, magnetic susceptibility and i.r. spectra.     

N,N,N′,N′-Tetramethylethylendiamin-di(tert-butyl)aluminium-Kationen — Molekülstruktur des [(Me3C)2Al · TMEDA]⊕[(Me3C)2AlBr2]⊖

(N,N,N′,N′ -tetramethylethylendiamine) di(tert-butyl)aluminium Cations — Molecular Structure of [(Me₃C)₂Al(TMEDA)]^⊕[(Me₃C)₂AlBr₂]^? Dimeric di(tert-butyl)aluminium halides (Me₃C)₂AlX (X = Cl, Br) react with N,N,N′,N′ -tetramethylethylendiamine (TMEDA) to give three compounds: the salt-like [(Me₃C)₂Al(TMEDA)]^⊕[(Me₃C)₂AlX₂]^? 1 , characterized by crystal structure determination, and [(Me₃C)₂Al(TMEDA)]^⊕X^? 3 both with chelating amine, and the more covalent, pentane soluble (Me₃C)₂AlX(TMEDA) 2 with TMEDA bound by only one nitrogen atom. The reaction resembles the symmetrical and unsymmetrical cleavage of diborane(6). 3 (X = Cl) is also formed by treatment of 1 with boiling n-hexane in the presence of TMEDA over a period of 24 hours, while for X = Br the more covalent 2 is the main product under similar conditions. In solution 2 decomposes slowly yielding different products in dependency of the solvent: in benzene 3 and in n-pentane 1 are formed.     

Magnesium tetraorganyl derivatives of group 13 metals as intermediate products in the synthesis of group 13 metal alkyls and aryls

Reactions of organomagnesium halides with group 13 metal halides lead to the formation of R₃M type compounds (R = alkyl, aryl; M = Al, Ga, In) and are considered as the simplest methods of R₃M compound syntheses. These seemingly simple reactions reveal a much more complex chemistry involving mixed magnesium-group 13 metal compounds. To elucidate the reaction course of reactions of organomagnesium halides with group 13 metal halides, we have studied reactions of R₃M with organomagnesium halides. The interaction of Et₃M with R¹MgX led to the formation of following products being mixtures of crystalline ionic complexes with the general composition of [Et_4-nR¹_nM]⁻[XMg (thf)₅]⁺·(thf): [Et_2.2Al(CH=CH₂)_1.8]⁻[BrMg (thf)₅]⁺·(thf) ( 1 ), [Et₃Ga(CH=CH₂)]⁻[BrMg (thf)₅]⁺·(thf) ( 2 ), [Et₄Al]⁻[BrMg (thf)₅]⁺·(thf) ( 3 ), [Et₄Ga]⁻[BrMg (thf)₅]⁺·(thf) ( 4 ), [Et_2.9Al(C₆H₅)_1.1]⁻[BrMg (thf)₅]⁺·(thf) ( 5 ), [Et_2.9Ga(C₆H₅)_1.1]⁻[BrMg (thf)₅]⁺·(thf) ( 6 ), [Et_3.4GaMe_0.6]⁻[IMg (thf)₅]⁺·(thf) ( 7 ) and [Et₄In]⁻[BrMg (thf)₅]⁺·(thf) ( 8 ). A comparison of the production course of group 13 metal trialkyls R₃M with a thermal decomposition of 1–8 products showed that reactions of MX₃ with RMgX (X = Br, I; R = alkyl, aryl) yield initially intermediate ionic compounds, which must then be thermally decomposed to obtain pure R₃M compounds. If group 13 metal bromides and iodides, and alkyl (aryl)magnesium bromides and iodides in thf are used, only intermediate products with the [R₄M]⁻[XMg (thf)₅]⁺·(thf) structure are formed.     

N-phosphonio formamidine derivatives: Synthesis,characterization, X-ray crystal structures,and deprotonation reactions

A simple and efficient method for the preparation of N-phosphonio formamidine derivatives of the general formula [R”₂N?C(H)=N?P(R’)R₂]⁺X^? is described. The data recorded in solution and the single crystal X-ray studies revealed that these compounds are best described by the combination of the two mesomeric N-phosphonio formamidine [R”₂N?C(H)=N?P(R’)R₂]⁺ and iminium phosphazene [R”₂N=C(H)?N=P(R’)R₂]⁺ forms. Formamidine phosphorus ylides ⁱPr₂N?C(H)=N?P(CH₂)R₂ were prepared after addition of ^tBuLi at –78 °C from the corresponding N-phosphonio compounds. [(PhCN)₂Pd(Cl)₂] was reacted with ⁱPr₂N?C(H)=N?P(CH₂)ⁱPr₂ to form the dimeric complex [(ⁱPr₂N?C(H)=N?P(CH₂)ⁱPr₂)Pd(Cl)(μ-Cl)]₂ which was structurally characterized by X-ray analysis. The deprotonation reactions conducted on [ⁱPr₂N?C(H)=N?PPh₃]⁺X^? occurred via an intramolecular rearrangement to give the cyanamide compound ⁱPr₂N?C≡N and PPh₃; transient formation of the amino-phosphazene-carbene ⁱPr₂N?C?N=PPh₃ was not observed.     

S4N3⊕[ReCl4(NSCl)2]⊖ Synthese und Kristallstruktur

S₄N₃^⊕[ReCl₄(NSCl)₂]^?. Synthesis and Crystal Structure S₄N₃^⊕[ReCl₄(NSCl)₂]^? is formed as a byproduct in the reaction of Re₂(CO)₁₀ with excess trithiazyl chloride. The compound is characterized by a crystal structure analysis by X-ray methods. S₄N₃[ReCl₄(NSCl)₂] crystallizes in the noncentrosymmetric space group P2₁2₁2₁ with four formula units per unit cell and the lattice dimensions a = 980, b = 1205, c = 1362 pm (2376 observed, independent reflexions; R = 0.076). The compound consists of the well known cyclic planar S₄N₃^⊕-cations and anions [ReCl₄(NSCl)₂]^?, in which the rhenium atom is coordinated octahedral by four Cl atoms and two cis-positioned NSCl ligands. The mean Re? N and N? S bond lengths (177 pm and 158 pm) correspond to double bonds. The bond lengths and angles are much like in the structure of AsPh₄[ReCl₄(NSCl)₂]; however the chlorine atoms of the NSCl ligands are turned to each other.     

Synthese und Kristallstruktur von SMe3 ⊕[MoBr4(SMe2)2]−

Synthesis and Crystal Structure of SMe₃^⊕ [MoBr₄(SMe₂)₂]^? . The title compound is obtained from MoBr₄ and excess dimethyl sulfide, forming red crystals which are only slightly sensitive to moisture. Whereas the intermediately formed adduct of MoBr₄ and SMe₂ is unstable, the stable adduct [Mo(NO)₂Br₂(SMe₂)₂] can be prepared from Mo(NO)₂Br₂ and SMe₂. According to the structural analysis by X-ray methods, SMe₃ ^⊕[MoBr₄(SMe₂)₂]^? crystallizes orthorhombic in the space group Imma with eight formula units per unit cell, the cell dimensions being a = 1578, b = 2820, c = 856 pm (1303 observed, independent reflexions). The compound consists of S(CH₃)₃^⊕ cations with S? C bond lengths of 180 pm and C? S? C bond angles of 102° and 103° resp., and anions [MoBr₄(SMe₂)₂]^?. The molybdenum atom is coordinated octahedral by four bromine atoms in equatorial positions and the two S atomes of the SMe₂ donor molecules in axial sites with Mo? S bond lengths of 254 pm.     

Darstellung und Schwingungsspektren von Dichloro- und Dibromodithiophosphat Die Kristallstrukturen von [PPh3Me] [PS2Cl2] und [PPh4] [PS2Br2]

Preparation and Vibrational Spectra of Dichloro and Dibromodithiophosphate. Crystal Structures of [PPh₃Me][PS₂Cl₂] and [PPh₄][PS₂Br₂] Dichloro and dibromodithiophosphates [Cat⁺][PS₂X₂^?] with a large organic cation can be obtained from P₄S₁₀, CatX and HX in CH₂Cl₂ (Cat⁺ = PPh₄⁺, PPh₃Me⁺; X = Cl, Br). The vibrational spectra (i.r. and Raman) of the [PS₂X₂]^? ions are reported and discussed; force constants were calculated. The crystal structures of [PPh₃Me][PS₂Cl₂] and [PPh₄][PS₂Br₂] were determined and refined with X-ray diffraction data. In both cases, simple anions [PS₂X₂]^? are present. [PPh₃Me][PS₂Cl₂]: orthorhombic, space group P2₁2₁2₁, a = 1089, b = 1334, c = 1476 pm, Z = 4, refinement to a residual index R = 0.046 for 1116 reflexions; the structure is isotopic with [PPh₃Me][VO₂Cl₂]. [PPh₄][PS₂Br₂]: tetragonal space group I4 , a = 1301, c = 721 pm, Z = 2, refinement to R = 0.065 for 357 reflexions; the structure is isotypic with [AsPh₄][FeCl₄] with [PS₂Br₂]^? ions occupying positions of 4 -symmetry with statistical orientation (statistical superposition of Br and S positions).     

Pt(II) ASSISTED DEOXYGENATION OF COORDINATED SULFOXIDES BY HYDROCHLORIC- OR HYDROBROMIC ACID

Abstract

The interaction of the complexes (Et₄ N)[Pt(R₂ SO)X₃] (R = Me, Et, CH₂ Ph, X [dbnd] C1; R [dbnd] Me, X [dbnd] Br) and cis-[Pt(Me₂ SO)₂ Cl₂] with concentrated HX (X [dbnd] Cl. Br) results in the reduction of the coordinated sulfoxides and oxidation of Pt(II) to Pt(IV). As a result [Pt(R₂ S)X₅ and [Pt(R₂S)₂ X₄] are formed. Ligands R₂ S can be removed from the complexes and isolated in a free state.     

Trialkylhydridoalanate RxR′3-xAlH⊖ [R = CMe3; R′ = CH(SiMe3)2]

Trialkylhydridoalanates R_xR′_3?xAlH^? [R = CMe₃; R′ = CH(SiMe₃)₂] The very strong base tert-butyl lithium reacts in the presence of chelating tetramethylethylendiamine with the aluminium organyls Al[CH(SiMe₃)₂]₂CMe₃ 1 and Al[CH(SiMe₃)₂](CMe₃)₂ 2 not under proton abstraction from the C? H acidic elementorganic substituent, but under β-elimination and addition of the thereby formed LiH to the coordinatively unsaturated aluminium atom. Two alanates — [Hal{CH(SiMe₃)₂}₂CMe₃]^? 3 and [HAl{CH(SiMe₃)₂}(CMe₃)₂]^? 4 each with Li(TMEDA)₂^⊕ as counterion — were isolated; they exhibit separate anions and cations in solid state as shown by a crystal structure determination on 3 . In absence of the chelating amine tert-butyl lithium decomposes under the catalytic effect of the aluminium compound to LiH, which does not add to aluminium and precipitates in a reactive form.     

Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts

In this work, we analyze the geometry and electronic structure of the [X_nM₃]^n?2 species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo‐[M₃]^2? unit. The cyclo‐[M₃]^2? ring is held together through a three‐center two‐electron bond of σ‐character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo‐[M₃]^2? ring and leads to a change from σ‐aromaticity in the bound state of the cyclo‐[M₃]^2? to π‐aromaticity in the XM₃^? and X₂M₃ metallic clusters. Our results also show that the aromaticity of the cyclo‐[M₃]^2? unit in the X₂M₃ metallic clusters depends on the nature of X and M. Moreover, we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M₃ ring. The Na₂Mg₃, Li₂Mg₃, and X₂Ca₃ clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M₃ ring, whereas X₂Be₃ and K₂Mg₃ keep its aromaticity relatively constant along this process. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Die Reaktion von [Mo6Cl8]X4 mit N-Basen

Reaction of [Mo₆Cl₈]X₄ with N-Bases [Mo₆Cl₈]X₄ (X = Cl, Br, I) in ethanol solution by titration with Ag⁺ showed 4 labil X atoms. The displacement of X^? especially by F^? accelerates the titration decisively. Conductivity measurements in ethanol or acetone showed that [Mo₆Cl₈]X₄ at 25°C behave as weak 1:1-electrolytes. Solutions of [Mo₆Cl₈]X₄ in DMF heated up to 60°C and than lowered to 25°C showed that the compounds in this solvent behave as (potential) strong 2:1-valent electrolytes. From the following compounds the labil halides have been determined by titration with Ag⁺: [Mo₆Cl₈]X₄(Py)₂ (X = Cl, Br), [Mo₆Cl₈]X₄(bipy)₂ (X = Cl, Br, I), [Mo₆Cl₈]X₄(Phenpy)₂ (X = Cl, Br, I), (PyH)₂[Mo₆Cl₈]X₆ (X = Cl, Br); (bipyH)₂[Mo₆Cl₈]I₄Cl₂. Always 4 (respectively 6) labil halides have been observed; exception [Mo₆Cl₈]Cl₄(Py)₂ in acetone (2 labil Cl). Lattice constants and mole volumina for the adducts with pyridin and bipyridin have been determined. The adducts with bipyridin and phenylpyridin are isotypic. Conductivity measurements have been made in different solutions. The decomposition on the thermobalance showed that in [Mo₆Cl₈]Cl₄(Py)₂ the bond of pyridin is weak. The 2 pyridin molecules are evolved at the same time. However [Mo₆Cl₈]I₄(Bipy)₂ loses 1 bipyridin only. (PyH)₂[Mo₆Cl₈]X₆ formed during the first decomposition step the novel compounds (PyH) [Mo₆Cl₈]X₅ (X = Cl, Br). Both compounds are isotypic. They behave in ethanol solution as strong 1:1-valent electrolytes.     

Crystal structures of binuclear Bi(III) chloride and bromide complexes with some cations — Alkylated pyridine derivatives

By a reaction of [BiX₆]^3– with salts of various N-alkylated pyridine derivatives in 2M HX (X = Cl, Br), (N-BzPy)₄[Bi₂X₁₀] complexes (X = Cl (1), Br (2), (4-MePyH)₄[Bi₂Cl₁₀] (3)) are obtained and structurally characterized.     

Synthese von Oxovanadium(V)‐halogeno‐Komplexen der tripodalen Sauerstoffliganden LR— = [η5‐(C5H5)Co{PR2(O)}3]—, R = OMe,OEt

Syntheses of Oxovanadium(V) Halide Complexes Stabilized with Tripodal Oxygen Ligands L_R^— = [η⁵‐(C₅H₅)Co{PR₂(O)}₃]^—, R = OMe, OEt The sodium salts of the tripodal oxygen ligands L_R^— = [η⁵‐(C₅H₅)Co{PR₂(O)}₃]^— (R = OMe, OEt) react with the oxovanadium halides V(O)F₃ and V(O)Cl₃ to yield deep red compounds of the type [V(O)X₂L_R]. Halide exchange reactions with [V(O)Cl₂L_OMe] und [V(O)F₂L_OMe] aiming at the preparation of the analogous bromide complex [V(O)Br₂L_OMe] led to the isomer [VO(L_OMe)₂][V(O)Br₄]. The crystal structure of [V(O)Cl₂L_OMe] has been determined by single crystal x‐ray diffraction. The compound crystallizes in the monoclinic space group P2₁/n with a = 9.6332(8), b = 15.0312(11) and c = 15.3742(12)Å, β = 100.181(8)°. The coordination around vanadium is distorted octahedral.