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Reactivity of the (trans-Pt(PMe3)2(C≡CC6H4SMe)2) Ligand with Copper Cyanide: Formation of the [Cu2(μ2-C≡CC6H4SMe)2]n Polymer

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Abstract

The organometallic ligand trans-Pt(PMe3)2(C≡CC6H4SMe)2, L1, reacts with C≡N− ions (as sodium salt) in various stoichiometric ratios to form L3, [trans-Pt(PMe3)2(C≡N)2], and MeSC6H4C≡C− anions, which were identified using various spectroscopic techniques (1H and 31P NMR, and ESI-TOF). Concurrently, the capture of the released MeSC6H4C≡C− units by Cu(I) metals was observed when L1 was reacted with CuCN in excess. In this case, two new coordination polymers (CPs), [Cu(μ2-C≡CC6H4SMe)]n (CP1) and [CuCN(L2)]n (CP2) where L2 is the new ligand [trans-Pt(PMe3)2(C≡CC6H4SMe)(C≡N)] formed along with the [trans-Pt(PMe3)2(C≡N)2] complex in small amount. CP1 was also synthesized independently to secure its identification. CP1 was found to be emissive at both 298 and 77 K. The nature of its emissive excited state was found to be an intraligand MeSC6H4C≡C−3ππ* mixed with some atomic contributions of the copper(I) d-orbitals based on DFT computations.

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This work was supported by the Natural Sciences and Engineering Research Council of Canada.

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    Frank Juvenal & Pierre D. Harvey

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Juvenal, F., Harvey, P.D. Reactivity of the (trans-Pt(PMe3)2(C≡CC6H4SMe)2) Ligand with Copper Cyanide: Formation of the [Cu2(μ2-C≡CC6H4SMe)2]n Polymer. J Inorg Organomet Polym 30, 159–168 (2020). https://doi.org/10.1007/s10904-019-01298-7

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