Synthesis of V/Fe/S Clusters Using Vanadium(III) Thiolate Complexes Bearing a Phenoxide-Based Tridentate Ligand

Vanadium­(III) thiolate complexes carrying a phenoxide-based tridentate ligand were prepared from the reactions of V­(NMe₂)₄ with the protonated forms of tridentate ligands (H₂­(O,P,O) = bis­(3,5-di-<i>tert</i>-butyl-2-hydroxy­phenyl)­phenylphosphine or H₂(O,O,O) = bis­(3,5-di-<i>tert</i>-butyl-2-hydroxy­phenyl)­phenyl­phosphine­oxide) and thiols (HSR; R = mesityl (Mes), 2,4,6-<i>ⁱ</i>Pr₃C₆H₂ (Tip)). The vanadium–thiolate complexes were subjected to the V/Fe/S cluster synthesis via treatment with an Fe­(II) thiolate complex [(TipS)­Fe]₂­(μ-SDmp)₂ (<b>4</b>, Dmp = 2,6-(mesityl)₂­C₆H₃) and elemental sulfur in toluene, leading to the formation of two new V/Fe/S clusters. One is an edge-bridged double-cubane-type [VFe₃S₄]-[VFe₃S₄] cluster [(O,P,O)­VFe₃S₄­(SDmp)­(HNMe₂)]₂ (<b>5</b>) having face-capping tridentate (O,P,O) ligands on vanadium atoms. The other is a [VFe₃S₄-Fe] cluster [(μ-O,O,O)­VFe₃S₄­(SDmp)­(STip)­Fe­(μ-SDmp)] (<b>6</b>), the core of which consists of a cubane-type [VFe₃S₄] unit and an external iron atom. The external iron is bound to an SDmp ligand and two oxygen atoms of the tridentate (O,O,O) ligand. Cluster <b>6</b> is structurally relevant to the active site of nickel-dependent CO dehydrogenase, and their common structural features include a cubane-type unit with a heterometal, one more iron atom besides the cubane unit, and a bridging ligand between the external iron and the heterometal of the cubane unit

Clinical Effect of Lenvatinib Re-Administration after Transcatheter Arterial Chemoembolization in Patients with Intermediate Stage Hepatocellular Carcinoma

The present study clarified the prognosis of intermediate-stage hepatocellular carcinoma (HCC) patients who received lenvatinib (LEN) followed by transcatheter arterial chemoembolization (TACE) on demand. We retrospectively evaluated 88 intermediate-stage HCC patients who received LEN. The median age was 74 (range: 47–92) years old, 67 patients were male, and 82 were classified as Child-Pugh A. LEN was administered until disease progression or discontinuation due to adverse events (AEs). The mean duration of LEN treatment was 7.0 months. The response and disease control rates were 51.1% and 89.8%, respectively. The median progression-free survival and overall survival (OS) after the initiation of LEN were 6.8 months and 29.9 months, respectively. The OS in patients for whom LEN was re-administered after TACE (TACE-LEN) was better than that in patients who received other therapies (e.g., only TACE, TACE-other therapy, or only other therapy) even with propensity score matching (p = 0.008). A Cox proportional hazard analysis showed that TACE-LEN was most strongly associated with the OS (hazard ratio: 0.083, 95% confidence interval: 0.019–0.362, p = 0.001). LEN was administered for approximately 11.1 months after TACE. In intermediate-stage HCC patients who can tolerate LEN without discontinuation due to AEs, TACE-LEN may prolong the prognosis