Thomas, J. Christopher and Peters, Jonas C. (2004) Platinum-alkyl and hydride complexes supported by a tris(phosphino)borate ligand: structural and spectroscopic studies. Polyhedron, 23 (2-3). pp. 489-497. ISSN 0277-5387. doi:10.1016/j.poly.2003.11.036. https://resolver.caltech.edu/CaltechAUTHORS:20140730-150704289
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Abstract
The synthesis and characterization of platinum-methyl and hydride complexes containing the ligand [PhBP_3] ([PhBP_3]=[PhB(CH_2PPh_2)_3]^−) are described. Metalation of [PhBP_3][TBA] (1[TBA], [TBA]=[nBu_4N]^+) with platinum methyl precursors provided the corresponding phosphine methyl platinum species [PhBP_3]PtMe_3 (2) and [[κ^2-PhBP_3]PtMe_2][TBA] (3). The reactivity of octahedral 2 and square planar 3 are discussed, and their X-ray diffraction structures are reported. Octahedral Pt(IV) 2 was found to be very thermally and chemically robust. In contrast, the square planar Pt(II) complex 3 demonstrated reactivity at both the platinum center and the unbound phosphine. The reaction of 3 with one equivalent of elemental sulfur provided the corresponding phosphine-sulfide [[κ^2-PhB(CH_2P(S)Ph_2)(CH_2PPh_2)_2]PtMe_2][TBA] (4). Similarly, the reaction of 3 with one equivalent of BH_3 • SMe_2 generated the borane-protected complex [[κ^2-PhB(CH_2P(BH_3)Ph_2)(CH_2PPh_2)_2]PtMe_2][TBA] (5). Complex 5 was significantly less reactive than 3 to a variety of substrates under similar conditions; however, the reaction of 5 with additional BH_3 • SMe_2 resulted in the formation of the platinum(I) bridged hydride species [[κ^2-PhB(CH_2P(BH_3)Ph_2)(CH_2PPh_2)_2]Pt(μ-H)]_2[TBA]_2 (6).
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| Additional Information: | © 2003 Elsevier Ltd. Received 30 July 2003; Accepted 8 October 2003. Larry Henling is acknowledged for his assistance with X-ray crystallography. Joseph Duimestra is acknowledged for assistance with the protocol for [PhBP3] [TBA]. J.C.T. is grateful to the NSF and to the Moore Foundation for graduate research fellowships. The authors acknowledge financial support from the NSF (CHE-0132216) and the DOE (PECASE). | |||||||||
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| Subject Keywords: | Zwitterions; Monoanionic ligands; Syntheses; Structures; Methyl; Hydrides | |||||||||
| Issue or Number: | 2-3 | |||||||||
| DOI: | 10.1016/j.poly.2003.11.036 | |||||||||
| Record Number: | CaltechAUTHORS:20140730-150704289 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20140730-150704289 | |||||||||
| Official Citation: | Thomas, J. C., & Peters, J. C. (2004). Platinum-alkyl and hydride complexes supported by a tris(phosphino)borate ligand: structural and spectroscopic studies. Polyhedron, 23(2–3), 489-497. doi: http://dx.doi.org/10.1016/j.poly.2003.11.036 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 47680 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Joanne McCole | |||||||||
| Deposited On: | 31 Jul 2014 15:49 | |||||||||
| Last Modified: | 10 Nov 2021 17:49 |
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