Issue 43, 2014

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

Abstract

The ligands 1,2-C6H4(CH2PtBu2)2 (La) and 1,2-C6H4(PtBu2)(CH2PtBu2) (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.

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

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
28 Jul 2014
Accepted
09 Sep 2014
First published
10 Sep 2014
This article is Open Access
Creative Commons BY license

Dalton Trans., 2014,43, 16335-16344

Author version available

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

S. J. K. Forrest, P. G. Pringle, H. A. Sparkes and D. F. Wass, Dalton Trans., 2014, 43, 16335 DOI: 10.1039/C4DT02303J

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