Catenated Compounds: Group 16 Elements Selenium and Tellurium

Laitinen, Risto S.; Oilunkaniemi, Raija

doi:10.1016/b978-0-12-409547-2.11532-x

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“…In contrast to the plethora of reports on the chemistry of transition metal–polysulfido complexes in general, the chemistries of polyselenides and polytellurides are comparatively less developed. ,,− While an appreciable number of transition metal–polyselenido and relatively a smaller number of transition metal–polytellurido compounds are now available in the literature, most of these examples feature either metal–polyselenido/polytellurido compounds having Se/Te/P-donor ligands − or only Se/Te-donor ligands (polyselenide/polytelluride) ,,− or organometallic compounds, ,,− while some other reports include [Fe(Se 3 )L 2 ] 1– (L = N (Dipp)SiMe 3 , Dipp = 2,6-diisopropylphenyl), [Cu 2 (Se 2 )(Bn 3 TACH) 2 ] 2+ and [Mn(dien) 2 ] 2 [SbSe 4 Cu(μ-Se 4 )] (dien = diethylenetriamine) . The majority of these metal–polychalcogenido compounds are organometallic compounds.…”

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confidence: 99%

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Hossain,

Roy Choudhury,

Majumdar

2024

JACS Au

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A series of six binuclear Co(II)−thiolate complexes, [Co 2 (BPMP)(S−C 6 H 4 -o-X) 2 ] 1+ (X = OMe, 2; NH 2 , 3), [Co 2 (BPMP)(μ-S−C 6 H 4 -o-O)] 1+ (4), and [Co 2 (BPMP)(μ-Y)] 1+ (Y = bdt, 5; tdt, 6; mnt, 7), has been synthesized from [Co 2 (BPMP)(MeOH) 2 (Cl) 2 ] 1+ (1a) and [Co 2 (BPMP)(Cl) 2 ] 1+ (1b), where BPMP 1− is the anion of 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol. While 2 and 3 could allow the two-electron redox reaction of the two coordinated thiolates with elemental sulfur (S 8 ) to generate [Co 2 (BPMP)(μ-S 5 )] 1+ (8), the complexes, 4−7, could not undergo a similar reaction. An analogous redox reaction of 2 with elemental selenium ([Se]) produced [{Co 2 (BPMP)(μ-Se 4 )}{Co 2 (BPMP)(μ-Se 3 )}] 2+ (9a) and [Co 2 (BPMP)(μ-Se 4 )] 1+ (9b). Further reaction of these polychalcogenido complexes, 8 and 9a/9b, with PPh 3 allowed the isolation of [Co 2 (BPMP)(μ-S)] 1+ (10) and [Co 2 (BPMP)(μ-Se 2 )] 1+ (11), which, in turn, could be converted back to 8 and 9a upon treatment with S 8 and [Se], respectively. Interestingly, while the redox reaction of the polyselenide chains in 9a and 11 with S 8 produced 8 and [Se], the treatment of 8 with [Se] gave back only the starting material (8), thus demonstrating the different redox behavior of sulfur and selenium. Furthermore, the reaction of 8 and 9a/9b with activated alkynes and cyanide (CN − ) allowed the isolation of the complexes, [Co 2 (BPMP)(μ-E 2 C 2 (CO 2 R) 2 )] 1+ (E = S: 12a, R = Me; 12b, R = Et; E = Se: 13a, R = Me; 13b, R = Et) and [Co 2 (BPMP)(μ-SH)(NCS) 2 ] (14), respectively. The present work, thus, provides an interesting synthetic strategy, interconversions, and detailed comparative reactivity of binuclear Co(II)−polychalcogenido complexes.

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