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Issue 13, 2019
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Chalcogen stabilized trimetallic clusters: synthesis, structures, and bonding of [(Cp*M)3(E)6+m(BH)n] (M = Nb or Ta; E = S or Se; m = 0 or 1 or 2; n = 0 or 1)

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Abstract

In an effort to isolate the chalcogen-rich niobium analogue of [(Cp*Ta)3(μ-S)33-S)3BH], the room temperature reaction of [Cp*NbCl4] (Cp* = η5-C5Me5) with Li[BH2S3] was carried out. Although the objective of isolating the niobium analogue was not achieved, the reaction yielded a homocubane-type cluster [(Cp*Nb)3(μ-S)33-S)3(μ-S)BH], 1, and a hexa-sulfido cluster [(Cp*Nb)3(μ-S)6], 2. Cluster 1 is a notable example of a homocubane-type cluster in which one of the vertices of the homocubane is missing. Compound 1 may be considered as a hypo-electronic cluster with an electron count of 64 cve (cve = cluster valence electrons), whereas compound 2 shows the presence of two doubly bridging η1-S around each Nb–Nb bond. On the other hand, the room temperature reaction of [Cp*TaCl4] with selenaborate ligand, [LiBH2Se3], led to the formation of [(Cp*Ta)3(μ-Se)4{μ-Se2(Se2)}], 3. Compound 3 is one of the rarest examples having a Ta3Se6 core structure with a unique diselenide bridging fragment. The presence of a short Se–Se bond of this diselenide unit makes this molecule of further interest. All these compounds were characterized by 1H, 11B{1H} and 13C{1H} NMR spectroscopy, infrared spectroscopy, mass spectrometry, and single-crystal X-ray crystallography. Density functional theory (DFT) calculations were carried out to provide insight into the bonding and electronic structures of these chalcogen-rich trimetallic clusters.

Graphical abstract: Chalcogen stabilized trimetallic clusters: synthesis, structures, and bonding of [(Cp*M)3(E)6+m(BH)n] (M = Nb or Ta; E = S or Se; m = 0 or 1 or 2; n = 0 or 1)

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Article information


Submitted
22 Dec 2018
Accepted
21 Feb 2019
First published
26 Feb 2019

Dalton Trans., 2019,48, 4203-4210
Article type
Paper

Chalcogen stabilized trimetallic clusters: synthesis, structures, and bonding of [(Cp*M)3(E)6+m(BH)n] (M = Nb or Ta; E = S or Se; m = 0 or 1 or 2; n = 0 or 1)

S. Kar, S. Bairagi, K. Saha, B. Raghavendra and S. Ghosh, Dalton Trans., 2019, 48, 4203
DOI: 10.1039/C8DT05061A

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