Sr3(BS3)2 und Sr3(B3S6)2: Zwei neue nicht‐oxidische Chalkogenoborate mit trigonal‐planar koordiniertem Bor

Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂ were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr₃(BS₃)₂ crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr₃(B₃S₆)₂ is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr₃(BS₃)₂ contains isolated [BS₃]^3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr₃(B₃S₆)₂ consists of cyclic [B₃S₆]^3— anions and strontium cations, respectively.     

Syntheses and Crystal Structures of the Novel Ternary Thioborates Na3BS3, K3BS3, and Rb3BS3

The orthothioborates Na₃BS₃, K₃BS₃ and Rb₃BS₃ were prepared from the metal sulfides, amorphous boron and sulfur in solid state reactions at temperatures between 923 and 973 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction experiments. Na₃BS₃ crystallizes in the monoclinic space group C2/c (No. 15) with a = 11.853(14) Å, b = 6.664(10) Å, c = 8.406(10) Å, β = 118.18(2)° and Z = 4. K₃BS₃ and Rb₃BS₃ are monoclinic, space group P2₁/c (No. 14) with a = 10.061(3) Å, b = 6.210(2) Å, c = 12.538(3) Å, β = 112.97(2) and a = 10.215(3) Å, b = 6.407(1) Å, c = 13.069(6) Å, β = 103.64(5)°, Z = 4. The potassium and rubidium compounds are not isotypic. All three compounds contain isolated [BS₃]^3– anions with boron in a trigonal‐planar coordination. The sodium cations in Na₃BS₃ are located between layers of orthothioborate anions, in the case of K₃BS₃ and Rb₃BS₃ stacks of [BS₃]^3– entities are connected via the corresponding cations. X‐ray powder patterns were measured and compared to calculated ones obtained from single crystal X‐ray structure determinations.     

Syntheses,Crystal Structures,and Properties of the Novel Thioborates KBa4(BS3)3 and K4Ba11(BS3)8S

Our systematic studies on quaternary thioborates containing both a comparably small alkali metal ion and a large alkaline earth cation lead to the two new crystalline phases KBa₄(BS₃)₃ and K₄Ba₁₁(BS₃)₈S. The former consists of isolated BS₃ units and the corresponding counter‐ions while in the latter BS₃^3– and S^2– anions coexist. In both compounds boron is found in a trigonal‐planar coordination, in the case of K₄Ba₁₁(BS₃)₈S the additional sulfide anions are located inside an octahedron built of six barium cations. The two compounds were prepared in solid state reactions from the metal sulfides, amorphous boron and sulfur. Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. KBa₄(BS₃)₃ crystallizes in the monoclinic space group C 2/c (no. 15) with a = 14.299(6) Å, b = 8.808(3) Å, c = 13.656(5) Å, β = 98.72(4)°, and Z = 4, while for K₄Ba₁₁(BS₃)₈S the trigonal space group R 3 c (no. 167) was found with a = 18.146(3) Å, c = 25.980(7) Å, and Z = 6. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination, in the case of K₄Ba₁₁(BS₃)₈S vibrational spectra were recorded.     

Na2B2S5 and Li2B2S5: Two Novel Perthioborates with Planar 1,2,4-Trithia-3,5-Diborolane Rings

For the first time perthioborates with trigonal planar coordination of boron were prepared. Na₂B₂S₅ (Pnma, a = 12.545(2) Å, b = 7.441(1) Å, c = 8.271(1) Å, Z = 4) and Li₂B₂S₅ (Cmcm, a = 15.864(1) Å, b = 6.433(1) Å, c = 6.862(1) Å, Z = 4) were obtained by reaction of the metal sulfides with stoichiometric amounts of boron and an excess of sulfur (effective molar ratio M:B:S = 1:1:4) at 600°C (650°C) and subsequent annealing. The non-isotypic structures contain exactly planar [B₂S₅]^2? groups consisting of five-membered B₂S₃ rings with one additional exocyclic sulfur on each of the boron atoms. The alkaline metal cations are four-coordinate (lithium) and (four + four)-coordinate (sodium) respectively.     

Novel Alkaline Earth Metal Chalcogenoborates: Syntheses and Crystal Structures of Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se

Systematic studies on quaternary thio‐ and selenoborates containing heavier alkaline earth metal cations led to the two new isotypic crystalline phases Sr_4.2Ba_2.8(BS₃)₄S and Ba₇(BSe₃)₄Se. Both compounds consist of trigonal‐planar BQ₃ (Q = S, Se) units, isolated Q^2– anions and the corresponding counter‐ions. The two new chalcogenoborates were prepared in solid state reactions from the metal sulfides (selenides), amorphous boron and sulfur (selenium). Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. Sr_4.2Ba_2.8(BS₃)₄S and Ba₇(BSe₃)₄Se crystallize in the monoclinic space group C2/c (no. 15) with a = 9.902(3) Å, b = 23.504(9) Å, c = 9.884(3) Å, β = 90.01(3)° and Z = 4 in the case of the thioborate, while for the selenoborate the lattice parameters a = 10.513(2) Å, b = 25.021(5) Å, c = 10.513(2) Å, β = 90.10(3)° were determined. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination.     

Cs2B2S4 – Ein Salz der dimeren Metathioborsäure

Cs₂B₂S₄ – A Derivative of the Dimeric Metathioboric Acid Cs₂B₂S₄ (structure: I4₁/acd; a = 7.270(1) Å, c = 35.737(7) Å; Z = 8; substructure: I4/mmm; a′ = 5.141(1) Å, c′ = 17.868(4) Å, Z = 2) is prepared by the reaction of cesium sulfide with stoichiometric amounts of boron and sulfur (effective molar ratio M:B:S = 2:2:4) at 600°C and subsequent annealing. The crystal structure contains isolated [B₂S₄]^2? groups consisting of four-membered B₂S₂ rings with two exocyclic sulfur atoms on each of the boron atoms. The cesium cations are nine-coordinate between these rings. The structural feature of two edge-sharing BS₃ groups forming an isolated anion appears for the first time in thioborate chemistry, although it is known as a part of the polymeric network in B₂S₃.     

LiBaBS3 und LiBaB3S6: Zwei neue quaternäre Thioborate mit trigonal-planar koordiniertem Bor

LiBaBS₃ and LiBaB₃S₆: Two New Quaternary Thioborates with Trigonally Coordinated Boron LiBaBS₃ (P2₁/c; a = 7.577(2) Å, b = 8.713(2) Å, c = 8.687(2) Å, β = 116.22(2)°; Z = 4) und LiBaB₃S₆ (Cc; a = 15.116(3) Å, b = 8.824(2) Å, c = 8.179(2) Å, β = 117.46(3)°; Z = 4) were prepared by reaction of stoichiometric amounts of the metal sulfides, boron, and sulfur at 750°C. The anionic part of the structure of the orthothioborate LiBaBS₃ consists of isolated planar [BS₃]^3? anions. The crystal structure of the metathioborate LiBaB₃S₆ contains [B₃S₆]^3? anions formed by six-membered B₃S₃ rings with three exocyclic sulfur atoms. The metal cations are situated between the anion units leading to a ninefold sulfur coordination of the barium atoms and to a fivefold (LiBaBS₃) and fourfold (LiBaB₃S₆) coordination of the lithium atoms.     

Fluoride und Fluorosäuren. IV. Kristallstrukturen von Bortrifluorid und seinen 1:1-Verbindungen mit Wasser und Methanol,Hydroxo- und Methoxotrifluoroborsäure

Fluorides and Fluoro Acids. IV. Crystal Structures of Boron Trifluoride and its 1:1 Compounds with Water and Methanol, Hydroxo- and Methoxotrifluoroboric Acid Solid boron trifluoride displays an enantiotropic phase transition α ? β at ?147°C. A further solid phase, γ-BF₃, is metastable or stable only just below the melting point. Its crystal structure was determined. It is monoclinic with space group P2₁/c, eight molecules in the unit cell and the lattice parameters a = 4.779, b = 14.00, c = 7.430 Å, β = 107.60° at ?131°C. Two independent trigonal planar molecules with a mean B? F bond length of 1.287 Å (1.319 Å after correction for thermal motion) form a three-dimensional packing connection with non-parallel molecular planes across intermolecular B···F contacts of in the average 2.690 Å, by which the boron atoms achieve a total coordination of five fluorine atoms with nearly trigonal bipyramidal geometry. — The crystal structures of hydroxotrifluoroboric acid (BF₃OH₂, monoclinic, P2₁/n, Z = 4, a = 7.641, b = 7.957, c = 4.864 Å, β = 94.80 at ?35°C) and methoxotrifluoroboric acid (BF₃O(CH₃)H, orthorhombic, Pbca, Z = 8, a = 7.054, b = 9.390, c = 11.547 Å at ?40°C) display unlimited three-dimensional and one-dimensional linking, respectively, of the molecules by hydrogen bonds O? H···F.     

Li3BS3 und LiSrBS3: Neue Orthothioborate mit trigonal-planar koordiniertem Bor

Li₃BS₃ and LiSrBS₃: New Orthothioborates with Trigonal Planar Boron Coordination We report on the two new orthothioborates Li₃BS₃ (Pnma; a = 8.144(1) Å, b = 10.063(2) Å, 6.161(1) Å; Z = 4) and LiSrBS₃ (Pnma; a = 7.557(1) Å, b = 9.083(2) Å, c = 7.049(1) Å: Z = 4). The two new phases were prepared by reaction of the metal sulfides, amorphous boron, and sulfur at 700°C. Both compounds contain isolated, planar [BS₃]^3?-anions. The lithium ions have fourfold (Li₃BS₃) and sixfold (LiSrBS₃) sulfur coordination, the strontium ion shows an eightfold sulfur coordination. The two compounds represent new A₃BX₃ resp. AA′BX₃ structure types.     

The First Rare Earth Metal Thioborate: Synthesis and Crystal Structure of EuB2S4

Systematic studies on thio‐ and selenoborates containing heavier metal cations led to the new crystalline phase EuB₂S₄. The crystal structure of the europium metathioborate reveals polymeric [(B₂S₄)^2—]_n anions and divalent Eu‐cations which are connected via ionic interactions. The building blocks of the anions consist of BS₄‐tetrahedra. Condensation of these BS₄‐tetrahedra leads to corner‐ and edge‐sharing 2D‐networks running parallel to (1 0 0). Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 990 K were applied. EuB₂S₄ crystallizes in the monoclinic space group P2₁/c (no. 14) with a = 6.4331(6)Å, b = 14.099(1)Å, c = 6.0731(6)Å, β = 110.55(8)° and Z = 4.     

A dimeric heteroleptic five‐coordinate zinc(II) complex containing a non‐motionally restricted N,N′‐heterocyclic ligand

The title compound, bis(μ‐1,2‐benzene­thiol­ato)‐1:2κ³S,S′:S′;2:1κ³S,S′:S′‐bis­[(2,2′‐bi­pyridine‐κ²N,N′)­zinc(II)], [Zn₂(μ‐C₆H₄S₂)₂(C₁₀H₈N₂)₂], crystallizes with the dinuclear mol­ecule located on a center of symmetry. The coordination geometry about the Zn atom is a modestly distorted trigonal bipyramid, with the axial ligating atoms at an angle of 170.81 (4)° and the angles in the equatorial plane in the range 112.94 (4)–129.95 (4)°. Weak π‐stacking interactions between bi­pyridine ligands on adjacent mol­ecules [interplanar spacing = 3.315 (3) Å] and a possible weak intermolecular C—H⋯S hydrogen bond (H⋯S = 2.84 Å) are seen in the crystal.     

Darstellung und Kristallstrukturen von Li4−2xSr2+xB10S19 (x ≈ 0,27) und Na6B10S18. Zwei neue Thioborate mit hochpolymeren Makrotetraeder-Netzwerken

Synthesis and Crystal Structures of Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27) and Na₆B₁₀S₁₈. Two Novel Thioborates with Highly Polymeric Macro-tetrahedral Networks Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27) and Na₆B₁₀S₁₈ were prepared from the reaction of strontium sulfide and lithium sulfide (sodium sulfide) with boron and sulfur at 700°C in graphitized silica tubes. Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27) crystallizes in the monoclinic space group P2₁/c with a = 10.919(2) Å, b = 13.590(3) Å, c = 16.423(4) Å, and β = 90.48(2)°, Na₆B₁₀S₁₈ in the tetragonal space group I4₁/acd with a = 14.415(3) Å, c = 26.137(4) Å. Both structures contain supertetrahedral B₁₀S₂₀ units which are linked through tetrahedral corners to form a three-dimensional polymeric network in the case of Na₆B₁₀S₁₈ and one-dimensional chains in the case of Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27). All boron atoms are in tetrahedral BS₄ coordination (B? S bond lengths vary from 1.879(5) to 1.951(5) Å (1.875(10) to 1.987(9) Å)). The strontium and lithium (sodium) cations are located within large channels formed by the anions.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Preparation and Structure Determination of SrMn2(PO4)2 and Redetermination of b ′‐Mn3(PO4)2

Pale rose single crystals of SrMn₂(PO₄)₂ were obtained from a mixture of SrCl₂ · 6 H₂O, Mn(CH₃COO)₂, and (NH₄)₂HPO₄ after thermal decomposition and finally melting at 1100 °C. The new crystal structure of strontium manganese orthophosphate [P‐1, Z = 4, a = 8.860(6) Å, b = 9.054(6) Å, c = 10.260(7) Å, α = 124.27(5)°, β = 90.23(5)°, γ = 90.26(6)°, 4220 independent reflections, R1 = 0.034, wR2 = 0.046] might be described as hexagonal close‐packing of phosphate groups. The octahedral, tetrahedral and trigonal‐bipyramidal voids within this [PO₄] packing provide different positions for 8‐ and 10‐fold [SrO_x] and distorted octahedral [MnO₆] coordination according to a formulation Mn Mn Mn Sr (PO₄)₄. Single crystals of β′‐Mn₃(PO₄)₂ (pale rose) were grown by chemical vapour transport (850 °C → 800 °C, P/I mixtures as transport agent). The unit cell of β′‐Mn₃(PO₄)₂ [P2₁/c, Z = 12, a = 8.948(2) Å, b = 10.050(2) Å, c = 24.084(2) Å, β = 120.50°, 2953 independent reflections, R1 = 0.0314, wR2 = 0.095] contains 9 independent Mn²⁺. The reinvestigation of the crystal structure led to distinctly better agreement factors and significantly reduced standard deviations for the interatomic distances.     

Na6[B18Se17]: The First Selenoborato‐closo‐dodecaborate with a Polymeric Chain Anion

Systematic studies on selenoborates containing a B₁₂ cluster entity and alkali metal cations led to the new crystalline phase Na₆[B₁₈Se₁₇] which consists of a icosahedral B₁₂ cluster completely saturated with trigonal‐planar BSe₃ units and sodium counter‐ions. Neighbouring cluster entities are connected in one direction via exocyclic selenium atoms forming the infinite chain anion ([B₁₈Se₁₆Se_2/2]^6–)_∞. The new chalcogenoborate was prepared in a solid state reaction from sodium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 850 °C. Na₆[B₁₈Se₁₇] crystallizes in the monoclinic space group C2/c (no. 15) with a = 18.005(4) Å, b = 16.549(3) Å, c = 11.245(2) Å, β = 91.35(3)° and Z = 4.     

Mono and Poly‐nuclear Silver(I) Complexes with Thiosaccharin and Triphenylphosphine. Synthesis,Spectroscopic and Structural Characterization of Thiosaccharinato‐bis(triphenylphosphine)silver(I) and Tetrakis{thiosaccharinato(triphenylphosphine)silver(I)}

The reaction of Ag₆(tsac)₆ ( 1 ) (tsac = thiosaccharinate anion) with triphenylphosphine gives rise to the already reported [Ag(tsac)(PPh₃)₃] complex ( 2 ) and to two new silver‐thiosaccharinate‐phosphine complexes, [Ag(tsac)(PPh₃)₂] ( 3 ) and [Ag₄(tsac)₄(PPh₃)₄] ( 4 ) (PPh₃= triphenylphosphine). Spectroscopic characterization was carried out using IR, UV‐Visible and NMR techniques and confirmed by single crystal X‐ray diffraction. In each complex a singular coordination mode for the thiosaccharinate ligand is observed. The most important features of the different coordination modes of the thionates are discussed. Compound 3 crystallizes in monoclinic system, space group Pn, with a = 11.2293(3) Å, b = 12.7282(3) Å, c = 13.6056(4) Å, β = 94.985(2)°, Z = 2; while crystals of compound 4 are monoclinic, space group P2₁/n, a = 15.024(3) Å, b = 14.681(3) Å, c = 21.914(4) Å, β = 95.31(3)°, Z = 2. The coordination around the silver atoms in both complexes consists of almost trigonal‐planar arrangements, AgP₂S in 3 and AgS₂P in 4 .     

The Crystal and Molecular Structure of γ‐P4S6

The crystal and molecular structure of γ‐P₄S₆ was determined from single‐crystal X‐ray diffraction. It crystallizes monoclinically in the space group P2₁/m (No. 11) with a = 6.627(3) Å, b = 10.504(7) Å, c = 6.878(3) Å, β = 90.18(4)°, V = 478.8(4) ų, and Z = 2. The structure consists of cage‐like P₄S₆ molecules with C_S symmetry arranged with the topology of a cubic close packing.     

Syntheses of Halogenated Polyhedral Phosphaboranes: Crystal Structure of conjuncto‐3,3′‐(closo‐1,2‐P2B4Br3)2

Co‐pyrolysis of B₂Br₄ with PBr₃ at 480 °C gave, in addition to the main product closo‐1,2‐P₂B₄Br₄, conjuncto‐3,3′‐(1,2‐P₂B₄Br₃)₂ ( 1 ) and the twelve‐vertex closo‐1,7‐P₂B₁₀Br₁₀ ( 2 ), both in low yields. X‐ray structure determination for 1 [triclinic, space‐group P1 with a = 7.220(2) Å, b = 7.232(2) Å, c = 8.5839(15) Å, α = 97.213(15)°, β = 96.81(2)°, γ = 94.07(2)° and Z = 1] confirmed that 1 adopts a structure consisting of two symmetrically boron–boron linked distorted octahedra with the bridging boron atoms in the 3,3′‐positions and the phosphorus atoms in the 1,2‐positions. The intercluster 2e/2c B–B bond length is 1.61(3) Å. The shortest boron–boron bond within the cluster framework is 1.68(2) Å located between the boron atoms antipodal to the phosphorus atoms. The icosahedral phosphaborane 2 was characterized by ¹¹B‐¹¹B COSY NMR spectroscopy showing cross peaks indicative for the isomer with the phosphorus atoms in 1,7‐positions. Both the X‐ray data of 1 and the NMR spectroscopic data of 1 and 2 give further evidence for the influence of an antipodal effect of heteroatoms to cross‐cage boron atoms and, vice versa, of an additional shielding of the phosphorus atoms caused by B‐Hal substitution at the boron positions trans to phosphorus.     

Cs3UP2S8, a Coordination Polymer Containing the Unprecedented [U=S]2+ Sulfidouranium(2+) Moiety

Although terminal chalcogeno ligands are well known for the group 5 and 6 transition metals, they are highly unusual for the oxophilic group 4 metals and unknown so far for the lanthanides or actinides. Cs₃UP₂S₈, is the first actinide compound containing a terminal M=S group. It was synthesized by reacting uranium metal, Cs₂S, S, and P₂S₅ in a 4:1:8:3 ratio at 700 °C in an eutectic LiCl/CsCl mixture. The crystal structure was determined by single‐crystal X‐ray diffraction techniques. Cs₃UP₂S₈ crystallizes in the rhombohedral space group R$\bar{3}$ [a = 15.5217(8) Å; c = 35.132(2) Å, V = 8305.0(8) ų, Z = 18]. The crystal structure is based on a tetrahedral network type, wherein the uranium atoms are coordinated by a unusual sulfido moiety and thiophosphate groups in a pseudo‐tetrahedral fashion. The U=S distance of 2.635(3) Å observed in the sulfide moiety is approx. 0.2 Å shorter than the average U–S single bond length, indicating a double‐bond type character.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.