Open-ended metallodithiolene complexes with the 1,2,4,5-tetrakis(diphenylphosphino)benzene ligand: modular building elements for the synthesis of multimetal complexes

Kumar, S., Selvachandran, M., Arumugam, K., Shaw, M. C., Wu, C., Maurer, M., Zhang, X., Sproules, S. , Mague, J. T. and Donahue, J. P. (2021) Open-ended metallodithiolene complexes with the 1,2,4,5-tetrakis(diphenylphosphino)benzene ligand: modular building elements for the synthesis of multimetal complexes. Inorganic Chemistry, 60(17), pp. 13177-13192. (doi: 10.1021/acs.inorgchem.1c01573) (PMID:34370468)

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Abstract

Open-ended, singly metalated dithiolene complexes with 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) are prepared either by ligand transfer to [Cl2M(tpbz)] from (R2C2S2)SnR′2 (R = CN, R′ = Me; R = Me, R′ = nBu) or by a direct reaction between tpbz and [M(S2C2R2)2] (M = Ni, Pd, Pt; R = Ph, p-anisyl) in a 1:1 ratio. The formation of dimetallic [(R2C2S2)M(tpbz)M(S2C2R2)] attends these syntheses in modest amounts, but the open-ended compounds are readily separated by silica chromatography. As affirmed by X-ray crystallographic characterization of numerous members of the set, the [(R2C2S2)M(tpbz)] compounds show dithiolene ligands in their fully reduced ene-1,2-dithiolate form conjoined with divalent Group 10 ions. Minor amounts of octahedral [(Ph2C2S2)2PtIV(tpbz)], a presumed intermediate, are isolated from the preparation of [(Ph2C2S2)PtII(tpbz)]. Heterodimetallic [(Ph2C2S2)Pt(tpbz)Ni(S2C2Me2)] is prepared from [(Ph2C2S2)PtII(tpbz)]; its cyclic voltammogram, upon anodic scanning, shows two pairs of closely spaced, but resolved, 1e– oxidations corresponding first to [R2C2S22–] – 1e– → [R2C2S•S–] and then to [R2C2S•S–] – 1e– → [R2(C═S)2]. The open diphosphine of [(R2C2S2)M(tpbz)] can be oxidized to afford open-ended [(R2C2S2)M(tpbzE2)] (E = O, S). Synthesis of the octahedral [(dppbO2)3Ni][I3]2 [dppbO2 = 1,2-bis(diphenylphosphoryl)benzene] suggests that the steric profile of [(R2C2S2)M(tpbzE2)] is moderated enough that three could be accommodated as ligands around a metal ion.

Item Type:Articles
Additional Information:The Louisiana Board of Regents [Grant LEQSF-(2002-03)- ENH-TR-67] and the National Science Foundation (Grant MRI 1228232 and 0619770) are thanked for funding of Tulane University’s X-ray crystallography and mass spectrometry instrumentation, and Tulane University is acknowledged for its ongoing assistance with operational costs for the X-ray diffraction facility. S.K. and J.P.D. gratefully acknowledge support for this project from the National Science Foundation (Grant CHE 1836569).
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Kumar, S., Selvachandran, M., Arumugam, K., Shaw, M. C., Wu, C., Maurer, M., Zhang, X., Sproules, S., Mague, J. T., and Donahue, J. P.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Inorganic Chemistry
Publisher:American Chemical Society
ISSN:0020-1669
ISSN (Online):1520-510X
Published Online:09 August 2021
Copyright Holders:Copyright © 2021 The Authors
First Published:First published60(17): 13177-13192
Publisher Policy:Reproduced under a Creative Commons License

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