Die Oxochlorovanadate PPh₄[VOCl₃OH], PPh₄[VOCl₄], (PPh₄ )₂ [VOCl₄ ]·2CH₃CN und (PPh₄)₂[VOCl₄]·CH₃CN mit auffälligen Abweichungen von der quadratisch-pyramidalen Anionenstruktur / The Oxochlorovanadates PPh₄[VOCl₃OH], PPh₄[VOCl₄], (PPh₄ )₂ [VOCl₄ ]·2CH₃CN and (PPh₄)₂[VO

Abstract

Trichloro-hydroxo-oxo-vanadate(V), Tetrachloro-oxo-vanadate(IV), Tetrachloro-oxo-vanadate(V), Crystal Structure Starting from vanadium which was not free of oxide, VC14 was prepared; its reaction with PPh4Cl in the presence of K2S5 in dichloromethane yielded PPh4[VOCl3OH]. From V 2S5, PPh4Cl and S2C12 in acetonitrile, sulfur crystallized first, then PPh4[VOCl4], and then (PPh4)2[VOCl4]-4CH3CN. Upon standing with the mother liquor at -18°C , the latter was con verted to (PPh4)2[VOCl4]-2CH3CN. According to its X-ray crystal structure determination, PPh4[VOCl3OH] (space group Pbca, a = 1105.5, b = 1920.8, c = 2242.8 pm, Z -8) has near ly square-pyramidal anions that are associated to chains by 0-H --C1 bridges. PPh4[VOCl4] is isotypic with AsPh4[VOCl4] and has strictly square-pyramidal anions (space group P4/n, a = 1254.0, c = 765.0 pm, Z = 2). In (PPh4)2[VOCl4]-4CH3CN (space group P T, a = 1281.3, b = 1276.6, c = 1841.5 pm, a = 84.11°, ß = 83.96, 7 = 64.31°, Z = 2) the square pyramid of the VOCl42-ion is distorted towards a trigonal-bipyramidal shape (C2v symmetry) ha ving trans-C 1VC1 angles of 145.88° and 156.87° and 0=V-C1 angles of 107° and 101.6°. In (PPh4)2[VOCl4]-2CH3CN (space group P \ a = 1017.1, b = 1029.3, c = 2416.0, a = 77.74°, ß = 79.99°, 7 = 78.94°, Z = 2), the VOCl4_~ structure is even closer to trigonal-bipyramidal, with trans-C1VC1 angles of 133.25° and 165.80° and 0=V-C1 angles of 113.3° and 97°.

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

“…The calculated and experimental g-values of a variety of vandyl and V(IV) qubits are given in Table 3. 43,53,70,[75][76][77] Their spin-phonon analyses are given in Figures S18(a-f) and Tables S9(a-f), and specific spin-phonon slopes and additional computational results are given in Table 6. Note, of the vandyl complexes considered here, VOPc, VO(acac)2, and [VO(cat)2] 2were geometry optimized.…”