Tweaking the charge transfer: bonding analysis of Bismuth(III) complexes with a flexidentate phosphane ligand

Réka Mokrai; Jamie Barrett; David C. Apperley; Zoltán Benkö; Dominikus Heift

doi:10.1021/acs.inorgchem.0c00734

Tweaking the charge transfer: bonding analysis of Bismuth(III) complexes with a flexidentate phosphane ligand

Réka Mokrai, Jamie Barrett, David C. Apperley, Zoltán Benkö, Dominikus Heift

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

1 Downloads (Pure)

Abstract

To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C6H4-o-CH2SCH3)3BiCln](3-n)+ (n = 0-3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative PÔåÆBi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C6H4-o-CH2SCH3)3Bi]3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.

Original language	English
Pages (from-to)	8916-8924
Journal	Inorganic Chemistry
Volume	59
Issue number	13
Early online date	12 Jun 2020
DOIs	https://doi.org/10.1021/acs.inorgchem.0c00734
Publication status	Published - 6 Jul 2020

Bibliographical note

Note: This work was supported by European Union COFUND/Durham Junior Research Fellowship under EU grant agreement number 609412, the ETH Zurich, a BME-Nanotechnology FIKP grant of EMMI (BME FIKP-NAT), NKFIH (PD 116329), a Janos Bolyai Research Scholarship, a UNKP-19-4-BME-422 grant, Varga József Alapítvány, and Pro Progressio Alapítvány.

Keywords

Chemistry

Access to Document

10.1021/acs.inorgchem.0c00734

Heift-D-47197-VoRFinal published version, 2.33 MBLicence: CC BY

https://doi.org/10.1021/acs.inorgchem.0c00734

Cite this

@article{ac6effbab413480095f892a63657f9ca,

title = "Tweaking the charge transfer: bonding analysis of Bismuth(III) complexes with a flexidentate phosphane ligand",

abstract = "To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C6H4-o-CH2SCH3)3BiCln](3-n)+ (n = 0-3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative P{\^O}{\aa}{\AE}Bi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C6H4-o-CH2SCH3)3Bi]3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.",

keywords = "Chemistry",

author = "R{\'e}ka Mokrai and Jamie Barrett and Apperley, \{David C.\} and Zolt{\'a}n Benk{\"o} and Dominikus Heift",

note = "Note: This work was supported by European Union COFUND/Durham Junior Research Fellowship under EU grant agreement number 609412, the ETH Zurich, a BME-Nanotechnology FIKP grant of EMMI (BME FIKP-NAT), NKFIH (PD 116329), a Janos Bolyai Research Scholarship, a UNKP-19-4-BME-422 grant, Varga J{\'o}zsef Alap{\'i}tv{\'a}ny, and Pro Progressio Alap{\'i}tv{\'a}ny.",

year = "2020",

month = jul,

day = "6",

doi = "10.1021/acs.inorgchem.0c00734",

language = "English",

volume = "59",

pages = "8916--8924",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Tweaking the charge transfer

T2 - bonding analysis of Bismuth(III) complexes with a flexidentate phosphane ligand

AU - Mokrai, Réka

AU - Barrett, Jamie

AU - Apperley, David C.

AU - Benkö, Zoltán

AU - Heift, Dominikus

N1 - Note: This work was supported by European Union COFUND/Durham Junior Research Fellowship under EU grant agreement number 609412, the ETH Zurich, a BME-Nanotechnology FIKP grant of EMMI (BME FIKP-NAT), NKFIH (PD 116329), a Janos Bolyai Research Scholarship, a UNKP-19-4-BME-422 grant, Varga József Alapítvány, and Pro Progressio Alapítvány.

PY - 2020/7/6

Y1 - 2020/7/6

N2 - To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C6H4-o-CH2SCH3)3BiCln](3-n)+ (n = 0-3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative PÔåÆBi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C6H4-o-CH2SCH3)3Bi]3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.

AB - To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C6H4-o-CH2SCH3)3BiCln](3-n)+ (n = 0-3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative PÔåÆBi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C6H4-o-CH2SCH3)3Bi]3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.

KW - Chemistry

U2 - 10.1021/acs.inorgchem.0c00734

DO - 10.1021/acs.inorgchem.0c00734

M3 - Article

SN - 0020-1669

VL - 59

SP - 8916

EP - 8924

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 13

ER -

Tweaking the charge transfer: bonding analysis of Bismuth(III) complexes with a flexidentate phosphane ligand

Abstract

Bibliographical note

Keywords

Access to Document

Fingerprint

Cite this