Structure and Magnetism of Dibridged Vanadium(IV) Hydrotris(pyrazolyl)borate Dimers

Abstract

The synthesis and characterization of four dinuclear V(IV) complexes are described: 1, [LVO(μ-(Ph)2PO2)LVO]; 2, [LVO(μ-(Ph)HPO2)2LVO]; 3, [LVO(μ-OH)2LVO]; and 4, [LVO(μ-OH)(μ-OAc)LVO] (where L = hydrotris(pyrazolyl)borate). X-ray crystal structural analysis of 1−4 gave the following parameters: 1, C46H46B2N14O6P2V2, P1̄, a = 12.249(2) Å, b = 13.951(3) Å, c = 16.391(3) Å, α = 93.95(3)°, β = 100.53(3)°, γ = 110.01(3)°, Z = 2; 2, C47H48B2N19O9P3V3, P1̄, a = 9.927(2) Å, b = 12.307(2) Å, c = 24.878(3) Å, α = 98.12(1)°, β = 100.79(1)°, γ = 91.05(1)°, Z = 2; 3, C22H28B2N14O4V2, Pbca, a = 10.698(1) Å, b = 15.414(3) Å, c = 17.865(3) Å, Z = 4; 4, C24H24B2N12O5V2, C2/c, a = 34.252(4) Å, b = 14.623(2) Å, c = 15.387(2) Å, β = 102.32(1)°, Z = 8. Magnetic measurements indicate that all the compounds except 4 are moderately antiferromagnetically coupled. A rationalization for the magnetic behavior of these and other complexes of this type based on a direct overlap model modulated by the conformation of the eight-membered V(μ-OXO)2V ring is proposed.

Organo‐Phosph(on/in)ate‐Bridged Dimers of Vanadium(IV) Complexes with the Kläui Ligand: Synthesis and Characterization

“…Results are summarized in Table 1, Table S1, and Figure S1. [11] Attempts to correlate the trends across several stereoelectronic parameters [19] show no obvious correlation with the observed electrochemical oxidations or the donor R groups on the bridging O-PRЈRЈЈ-O unit. Most dimer complexes exhibited two unique oxidation events, believed to correspond to the one electron oxidation of one metal center in the dinuclear species (namely V IV /V IV to V IV /V V ) followed by the subsequent oxidation of the second vanadium center (i.e.…”

“…The molecule crystallizes in the triclinic space group P1 with two molecules per unit cell. [5,10,11,21] (CpP OMe Co)VOCl·H 2 O (4) crystallizes in the monoclinic space group P2 1 /n with four molecules of 4 per unit cell. 2.0 Å, one short vanadyl bond, and one long V···O interaction trans to the vanadyl.…”

“…(CpP OMe Co) 2 [μ-O 2 P(OH)(4-NO 2 PhO)] 2 V 2 O 2(11): An amount of 0.323 g (0.492 mmol) of (CpP OMe CO)VOCl·H 2 O (4) was dissolved in 15 mL of H 2 O to give a green solution. IR (solid): ν max = 2945, 2837, 1590, 1515, 1492, 1450, 1423, 1338, 1299, 1261, 1174, 1118, 1109, 1076, 1032, 1001, 951, 893, 862, 847, 838, 780, 726, 699, 628, 607, 589 cm -1 .…”

X-ray characterization of HnacnacR and the first vanadium β-diiminate dimer (R = mesityl)

“…Selected bond distances and angles for 2 are listed in table 3. The vanadyl, V¼O, bond length in 2 (1.594(2) Å ) is typical of (14) N1-C10-C12- Vanadium -diiminate dimer 2375 complexes of this type [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39]. A displacement ellipsoid plot for 2 is shown in figure 3.…”

Synthesis And Characterization Of A Series Of Vanadium(iv) Complexes With The Kläui Ligand

“…Further interest arises from the small possible cage-like vanadium phosphate clusters that have been observed to form around a variety of template molecules or ions. Carrano and co-workers employed a nitrogen tridentate ligand, hydridotris(pydazolyl)borate, HB(pz)3or Tp -, shown in Figure 8, to synthesize and characterize vanadium clusters (59,(63)(64)(65). Tpligand can serve as a facially coordinating, anionic six-electron donor (66)(67)(68).…”