X-Ray crystallographic structure of Ga8(pz)12O4Cl4·2thf: a novel gallium pyrazololate complex with a Ga4O4 core

Single-Ion versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)-Oxo Clusters: A Case Study

“…To our knowledge, the six‐membered cyclic structure of 2 is unprecedented among oxo‐bridged gallium( III ) clusters. These include the trimeric μ 3 ‐oxo‐centered carboxylate [Ga 3 (O)(O 2 CPh) 6 (4‐Me‐py) 3 ] + ,19a the tetranuclear complex [Ga 4 (OH) 6 (3‐ t Bu‐Hpz) 10 ] 6+ with a “butterfly” core,19b and the octagallium( III ) cluster [Ga 8 (pz) 12 O 4 Cl 4 ] (Hpz=pyrazole) 20. In the latter, four penta‐coordinated gallium( III ) ions are connected to an inner Ga 4 O 4 cubane core through μ 4 ‐oxo and pyrazolato bridges.…”

“…These include the trimeric m 3 -oxo-centered carboxylate [Ga 3 (O)(O 2 CPh) 6 (4-Me-py) 3 ] , [19a] the tetranuclear complex [Ga 4 (OH) 6 (3-tBu-Hpz) 10 ] 6 with a ªbutterflyº core, [19b] and the octagallium(iii) cluster [Ga 8 (pz) 12 pyrazole). [20] In the latter, four penta-coordinated gallium(iii) ions are connected to an inner Ga 4 O 4 cubane core through m 4oxo and pyrazolato bridges.…”

Coordination Versatility of Pyrazole‐Based Ligands towards High‐Nuclearity Transition‐Metal and Rare‐Earth Clusters

“…Antiferromagnetic interactions between the copper(II) ions were found in all compounds, and the variation of the magnetic exchange interaction is in agreement with magnetostructural correlations on the basis of the Cu-O-Cu angles (the so-called Haase correlation) [94] for the [Cu 4 (µ 3 -OR) 4 ] 4+ and [Cu 2 (µ-OH)] 3+ species, leading to a ground state of S T = 1/2. [97] Other examples of octanuclear clusters involve molybdenum(V/VI) [98] or zinc(II) ions. [95] This compound is the first example of an all-iron(III) cubane.…”

“…DFT studies were performed to confirm the parameters obtained from a fit of the experimental magnetic susceptibility data 96. A gallium(III) analogue was synthesized 97. Other examples of octanuclear clusters involve molybdenum(V/VI)98 or zinc(II) ions 99.…”

Synthesis and X-ray crystallographic structure of Ga4(OH)6(3-ButpzH)10I6·2MeCN: a quasi double heterocubane

“…In a previous publication we reported the reaction of Na[Me-Ga(pz) 3 ] with GaCl 3 to give Ga 8 (pz) 12 O 4 Cl 4 •2THF, which is based on a Ga 4 O 4 core. 1 However, this core contains edge bridging groups and we therefore refer to this and analogous structures as 'non-discrete'. 'Discrete' Ga 4 N 4 , Ga 4 S 4 , Ga 4 Se 4 and Ga 4 Te 4 cubanes are known, 2,3 but to date no 'discrete' Ga 6 As an extension of our work on Ga/O cubanes we attempted to synthesise a 'discrete' Ga 4 O 4 cubane by replacing Na[Me-Ga(pz) 3 ] with K[HB(3-Bu t pz) 3 ], thus eliminating the possibility of Ga-pz bridging, and GaCl 3 with GaI 3 , since I 2 is a better leaving group than Cl 2 .…”