Issue 13, 2019

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)

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)

Supplementary files

Article information

Article type
Paper
Submitted
22 Dec. 2018
Accepted
21 Febr. 2019
First published
26 Febr. 2019

Dalton Trans., 2019,48, 4203-4210

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements