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

Matthew S. Winston; John E. Bercaw

doi:10.1021/om100775g

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

Matthew S. Winston, John E. Bercaw

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

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.

Original language	English (US)
Pages (from-to)	6408-6416
Number of pages	9
Journal	Organometallics
Volume	29
Issue number	23
DOIs	https://doi.org/10.1021/om100775g
State	Published - Dec 13 2010
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: We thank Taylor N. Lenton, Yuxiao Sun, and Ian A. Tonks for helpful discussions and for comparisons to their unpublished results.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).
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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

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. {\textcopyright} 2010 American Chemical Society.",

author = "Winston, {Matthew S.} and Bercaw, {John E.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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). This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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doi = "10.1021/om100775g",

language = "English (US)",

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T1 - A Novel Bis(phosphido)pyridine [PNP] 2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes

AU - Winston, Matthew S.

AU - Bercaw, John E.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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). This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2010/12/13

Y1 - 2010/12/13

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/597358

UR - https://pubs.acs.org/doi/abs/10.1021/om100775g

UR - http://www.scopus.com/inward/record.url?scp=78649834444&partnerID=8YFLogxK

U2 - 10.1021/om100775g

DO - 10.1021/om100775g

M3 - Article

SN - 0276-7333

VL - 29

SP - 6408

EP - 6416

JO - Organometallics

JF - Organometallics

IS - 23

ER -

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

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