Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines

Qian Liao; Tianbiao Liu; Samantha I. Johnson; Christina M. Klug; Eric S. Wiedner; R. Morris Bullock; Daniel L. Dubois

doi:10.1039/c9dt00708c

Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines

Qian Liao, Tianbiao Liu, Samantha I. Johnson, Christina M. Klug, Eric S. Wiedner, R. Morris Bullock, Daniel L. Dubois

Pacific Northwest National Laboratory

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

5 Citations (Scopus)

Abstract

The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing P ^R ₂ N ^R′ ₂ ligands, which have been shown to be highly active H ₂ oxidation/production catalysts. A series of [Fe(P ^Ph ₂ N ^Bn ₂ ) ₂ (X)(Y)] ⁿ⁺ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact. The solid state structure of cis-Fe(P ^Ph ₂ N ^Bn ₂ ) ₂ Cl ₂ reveals that the six-membered rings adjacent to the P atoms are in a boat confirmation, resulting in close N⋯P distances that suggests the P atoms have a greater affinity for the lone pair of electrons on the N atom than chloride ligands. Similarly, boat conformations are observed for both rings adjacent to the hydride ligands of trans-[HFe(P ^Ph ₂ N ^Bn ₂ ) ₂ (CH ₃ CN)] ⁺ and trans-HFe(P ^Ph ₂ N ^Bn ₂ ) ₂ Cl, resulting in short N⋯H distances. Spectroscopic and computational studies of trans-[HFe(P ^Ph ₂ N ^Bn ₂ ) ₂ (CO)] ⁺ , trans-[HFe(P ^Ph ₂ N ^Bn ₂ )(P ^Ph ₂ N ^Bn ₂ H)(CO)] ²⁺ , and trans-[HFe(P ^Ph ₂ N ^Bn ₂ ) ₂ (H ₂ )] ⁺ indicate the complexes are more stable when the pendant amines in boat conformations are adjacent to the hydride ligand. These data suggest an attractor ordering of H ^- > CO > H ₂ > PR ₃ > Cl ^- ∼ CH ₃ CN.

Original language	English
Pages (from-to)	4867-4878
Number of pages	12
Journal	Dalton Transactions
Volume	48
Issue number	15
DOIs	https://doi.org/10.1039/c9dt00708c
Publication status	Published - 2019

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

10.1039/c9dt00708c

Fingerprint Dive into the research topics of 'Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines'. Together they form a unique fingerprint.

Cite this

Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines. / Liao, Qian; Liu, Tianbiao; Johnson, Samantha I.; Klug, Christina M.; Wiedner, Eric S.; Morris Bullock, R.; Dubois, Daniel L.

In: Dalton Transactions, Vol. 48, No. 15, 2019, p. 4867-4878.

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

@article{3222eabe470f4fdca9b2c2d192d44800,

title = "Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines",

abstract = " The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing P R 2 N R′ 2 ligands, which have been shown to be highly active H 2 oxidation/production catalysts. A series of [Fe(P Ph 2 N Bn 2 ) 2 (X)(Y)] n+ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact. The solid state structure of cis-Fe(P Ph 2 N Bn 2 ) 2 Cl 2 reveals that the six-membered rings adjacent to the P atoms are in a boat confirmation, resulting in close N⋯P distances that suggests the P atoms have a greater affinity for the lone pair of electrons on the N atom than chloride ligands. Similarly, boat conformations are observed for both rings adjacent to the hydride ligands of trans-[HFe(P Ph 2 N Bn 2 ) 2 (CH 3 CN)] + and trans-HFe(P Ph 2 N Bn 2 ) 2 Cl, resulting in short N⋯H distances. Spectroscopic and computational studies of trans-[HFe(P Ph 2 N Bn 2 ) 2 (CO)] + , trans-[HFe(P Ph 2 N Bn 2 )(P Ph 2 N Bn 2 H)(CO)] 2+ , and trans-[HFe(P Ph 2 N Bn 2 ) 2 (H 2 )] + indicate the complexes are more stable when the pendant amines in boat conformations are adjacent to the hydride ligand. These data suggest an attractor ordering of H - > CO > H 2 > PR 3 > Cl - ∼ CH 3 CN. ",

author = "Qian Liao and Tianbiao Liu and Johnson, {Samantha I.} and Klug, {Christina M.} and Wiedner, {Eric S.} and {Morris Bullock}, R. and Dubois, {Daniel L.}",

note = "Funding Information: This work was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. DOE. Computations were performed using the Cascade supercomputer at the Environmental Molecular Sciences Laboratory, a National Scientific User Facility sponsored by the DOE{\textquoteright}s Office of Biological and Environmental Research and located at PNNL. We thank Dr Mary Rakowski DuBois for helpful discussions. Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9dt00708c",

language = "English",

volume = "48",

pages = "4867--4878",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "15",

}

TY - JOUR

T1 - Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines

AU - Liao, Qian

AU - Liu, Tianbiao

AU - Johnson, Samantha I.

AU - Klug, Christina M.

AU - Wiedner, Eric S.

AU - Morris Bullock, R.

AU - Dubois, Daniel L.

N1 - Funding Information: This work was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. DOE. Computations were performed using the Cascade supercomputer at the Environmental Molecular Sciences Laboratory, a National Scientific User Facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. We thank Dr Mary Rakowski DuBois for helpful discussions. Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing P R 2 N R′ 2 ligands, which have been shown to be highly active H 2 oxidation/production catalysts. A series of [Fe(P Ph 2 N Bn 2 ) 2 (X)(Y)] n+ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact. The solid state structure of cis-Fe(P Ph 2 N Bn 2 ) 2 Cl 2 reveals that the six-membered rings adjacent to the P atoms are in a boat confirmation, resulting in close N⋯P distances that suggests the P atoms have a greater affinity for the lone pair of electrons on the N atom than chloride ligands. Similarly, boat conformations are observed for both rings adjacent to the hydride ligands of trans-[HFe(P Ph 2 N Bn 2 ) 2 (CH 3 CN)] + and trans-HFe(P Ph 2 N Bn 2 ) 2 Cl, resulting in short N⋯H distances. Spectroscopic and computational studies of trans-[HFe(P Ph 2 N Bn 2 ) 2 (CO)] + , trans-[HFe(P Ph 2 N Bn 2 )(P Ph 2 N Bn 2 H)(CO)] 2+ , and trans-[HFe(P Ph 2 N Bn 2 ) 2 (H 2 )] + indicate the complexes are more stable when the pendant amines in boat conformations are adjacent to the hydride ligand. These data suggest an attractor ordering of H - > CO > H 2 > PR 3 > Cl - ∼ CH 3 CN.

AB - The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing P R 2 N R′ 2 ligands, which have been shown to be highly active H 2 oxidation/production catalysts. A series of [Fe(P Ph 2 N Bn 2 ) 2 (X)(Y)] n+ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact. The solid state structure of cis-Fe(P Ph 2 N Bn 2 ) 2 Cl 2 reveals that the six-membered rings adjacent to the P atoms are in a boat confirmation, resulting in close N⋯P distances that suggests the P atoms have a greater affinity for the lone pair of electrons on the N atom than chloride ligands. Similarly, boat conformations are observed for both rings adjacent to the hydride ligands of trans-[HFe(P Ph 2 N Bn 2 ) 2 (CH 3 CN)] + and trans-HFe(P Ph 2 N Bn 2 ) 2 Cl, resulting in short N⋯H distances. Spectroscopic and computational studies of trans-[HFe(P Ph 2 N Bn 2 ) 2 (CO)] + , trans-[HFe(P Ph 2 N Bn 2 )(P Ph 2 N Bn 2 H)(CO)] 2+ , and trans-[HFe(P Ph 2 N Bn 2 ) 2 (H 2 )] + indicate the complexes are more stable when the pendant amines in boat conformations are adjacent to the hydride ligand. These data suggest an attractor ordering of H - > CO > H 2 > PR 3 > Cl - ∼ CH 3 CN.

UR - http://www.scopus.com/inward/record.url?scp=85064152254&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85064152254&partnerID=8YFLogxK

U2 - 10.1039/c9dt00708c

DO - 10.1039/c9dt00708c

M3 - Article

C2 - 30882832

AN - SCOPUS:85064152254

VL - 48

SP - 4867

EP - 4878

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 15

ER -

Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Cite this