Reversible CO exchange at platinum(0). An example of similar complex properties produced by ligands with very different stereoelectronic characteristics

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Abstract

The ligands 1,2-C6H4(CH2Pt Bu2)2 (La) and 1,2-C6H4(Pt Bu2)(CH2Pt Bu2) (Lb) displace norbornene (nbe) from [Pt(η2 -nbe)3] to give [PtL(η2 -nbe)] where L = La (1a) or Lb (1b); 1a is fluxional on the NMR timescale. Reaction of 1a, b with CO gives the corresponding monocarbonyls [PtL(CO)] where L = La (2a) or Lb (2b) which then react further, and reversibly, to give the dicarbonyls [PtL(CO)2] where L = La (3a) or Lb (3b). The CO interchange between 2a, b and 3a, b is compared with the only other such system (2f and 3f), which are complexes of (C2F5)2PCH2CH2P(C2F5)2 (Lf). Ethene reacts smoothly with 2a to give (4a) and H2 with 2a generates some [PtH2(La)]. Protonation of 2a gives [Pt(La)(H)(CO)][B(C6F5)4] (5a) whose crystal structure has been determined. Similarly protonation of 2b gives [Pt(Lb)(H)(CO)][B(C6F5)4] as a mixture of geometric isomers 5b–6b. © 2014 The Partner Organisations.

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Forrest, S. J. K., Pringle, P. G., Sparkes, H. A., & Wass, D. F. (2014). Reversible CO exchange at platinum(0). An example of similar complex properties produced by ligands with very different stereoelectronic characteristics. Journal of the Chemical Society. Dalton Transactions, 43(43), 16335–16344. https://doi.org/10.1039/c4dt02303j

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