A Novel Bis(phosphido)pyridine [PNP] 2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes

Handle URI:
http://hdl.handle.net/10754/597358
Title:
A Novel Bis(phosphido)pyridine [PNP] 2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes
Authors:
Winston, Matthew S.; Bercaw, John E.
Abstract:
A novel PNP bis(secondary phosphine)pyridine pincer ligand, 2,6-bis(2-(phenylphosphino)phenyl)pyridine, has been prepared in high yield, and the properties of the doubly deprotonated form as a ligand in K 4(PNP)2(THF)6 and (PNP)Zr(NMe2) 2 have been investigated. The neutral PNP ligand has been isolated as a mixture of noninterconverting diastereomers, due to the presence of two chirogenic phosphorus atoms of the secondary phopshines, but coordination of the dianionic form to potassium and zirconium allows for isolation of a single diastereomer in near-quantitative yield. The structure of a bis(dimethylamido) zirconium(IV) derivative of the bis(phosphido)pyridine ligand and DFT calculations suggest that the phosphides do not π-bond to early transition metals, likely due to geometric strain and possibly orbital size mismatch between phosphorus and zirconium. As a result, the soft phosphides are prone to formation of insoluble oligomers with substantial bridging of the phosphido lone pairs to other zirconium centers. © 2010 American Chemical Society.
Citation:
Winston MS, Bercaw JE (2010) A Novel Bis(phosphido)pyridine [PNP] 2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes . Organometallics 29: 6408–6416. Available: http://dx.doi.org/10.1021/om100775g.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
13-Dec-2010
DOI:
10.1021/om100775g
Type:
Article
ISSN:
0276-7333; 1520-6041
Sponsors:
We thank Taylor N. Lenton, Yuxiao Sun, and Ian A. Tonks for helpful discussions and for comparisons to their unpublished results. DFT calculations were carried out using the Molecular Graphics and Computation Facility, College of Chemistry, University of California, Berkeley, CA, with equipment support from NSF Grant CHE- 0233882. We gratefully acknowledge the support of the KAUST Center-In-Development at King Fand University of Petroleum and Minerals (Dhahran, Saudi Arabia) and the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431). We thank Lawrence M. Henling and Michael W. Day of Caltech for mounting crystals and solving their structures. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (Grant CHE-0639094).
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Full metadata record

DC FieldValue Language
dc.contributor.authorWinston, Matthew S.en
dc.contributor.authorBercaw, John E.en
dc.date.accessioned2016-02-25T12:31:30Zen
dc.date.available2016-02-25T12:31:30Zen
dc.date.issued2010-12-13en
dc.identifier.citationWinston MS, Bercaw JE (2010) A Novel Bis(phosphido)pyridine [PNP] 2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes . Organometallics 29: 6408–6416. Available: http://dx.doi.org/10.1021/om100775g.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/om100775gen
dc.identifier.urihttp://hdl.handle.net/10754/597358en
dc.description.abstractA novel PNP bis(secondary phosphine)pyridine pincer ligand, 2,6-bis(2-(phenylphosphino)phenyl)pyridine, has been prepared in high yield, and the properties of the doubly deprotonated form as a ligand in K 4(PNP)2(THF)6 and (PNP)Zr(NMe2) 2 have been investigated. The neutral PNP ligand has been isolated as a mixture of noninterconverting diastereomers, due to the presence of two chirogenic phosphorus atoms of the secondary phopshines, but coordination of the dianionic form to potassium and zirconium allows for isolation of a single diastereomer in near-quantitative yield. The structure of a bis(dimethylamido) zirconium(IV) derivative of the bis(phosphido)pyridine ligand and DFT calculations suggest that the phosphides do not π-bond to early transition metals, likely due to geometric strain and possibly orbital size mismatch between phosphorus and zirconium. As a result, the soft phosphides are prone to formation of insoluble oligomers with substantial bridging of the phosphido lone pairs to other zirconium centers. © 2010 American Chemical Society.en
dc.description.sponsorshipWe thank Taylor N. Lenton, Yuxiao Sun, and Ian A. Tonks for helpful discussions and for comparisons to their unpublished results. DFT calculations were carried out using the Molecular Graphics and Computation Facility, College of Chemistry, University of California, Berkeley, CA, with equipment support from NSF Grant CHE- 0233882. We gratefully acknowledge the support of the KAUST Center-In-Development at King Fand University of Petroleum and Minerals (Dhahran, Saudi Arabia) and the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431). We thank Lawrence M. Henling and Michael W. Day of Caltech for mounting crystals and solving their structures. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (Grant CHE-0639094).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleA Novel Bis(phosphido)pyridine [PNP] 2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexesen
dc.typeArticleen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionCalifornia Institute of Technology, Pasadena, United Statesen
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