The versatility of the boronyl (BO) and fluoroborylene (BF) ligands in binuclear cyclopentadienylpalladium chemistry

Hongxia Zhao; Aiping Peng; Xiuhui Zhang; Qian Shu Li; R. Bruce King

doi:10.1016/j.ica.2013.04.043

The versatility of the boronyl (BO) and fluoroborylene (BF) ligands in binuclear cyclopentadienylpalladium chemistry

Hongxia Zhao
, Aiping Peng
, Xiuhui Zhang^*
, Qian Shu Li
, R. Bruce King

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Beijing Institute of Technology
South China Normal University
University of Georgia

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

3 Citations (Scopus)

Abstract

The organometallic compounds Cp₂Pd₂(BO)₂ and Cp₂Pd₂(BF)₂ have been investigated by the MPW1PW91 and BP86 density functional methods. The potential energy surface of Cp₂Pd₂(BO)₂ is found to be relatively complicated with 11 structures within 20 kcal/mol (MPW1PW91) or 26 kcal/mol (BP86) of the global minimum. This cornucopia of Cp₂Pd ₂(BO)₂ structures includes both perpendicular and coaxial structures exhibiting a variety of different coordination modes of the BO groups. These Cp₂Pd₂(BO)₂ structures even include several structures with the BO group directly bonded to a Cp carbon atom. The Cp₂Pd₂(BF)₂ potential surface is considerably simpler than that of Cp₂Pd₂(BO)₂. Thus a coaxial Cp₂Pd₂(μ-BF)₂ structure with bridging BF groups and a Pd-Pd single bond of ∼2.67 Å is highly favored, lying more than 18 kcal/mol below any of the next lowest energy Cp ₂Pd₂(BF)₂ structures. This Cp ₂Pd₂(μ-BF)₂ structure is closely related to the known structure of the stable compound (η⁵-M _e5C₅)₂Pd₂(μ-CO)₂, which has been structurally characterized by X-ray crystallography.

Original language	English
Pages (from-to)	285-292
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	406
DOIs	https://doi.org/10.1016/j.ica.2013.04.043
Publication status	Published - 2013

Keywords

Boronyl
Cyclopentadienyl
Density functional theory
Fluoroborylene
Metal-metal bonding
Palladium

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title = "The versatility of the boronyl (BO) and fluoroborylene (BF) ligands in binuclear cyclopentadienylpalladium chemistry",

abstract = "The organometallic compounds Cp2Pd2(BO)2 and Cp2Pd2(BF)2 have been investigated by the MPW1PW91 and BP86 density functional methods. The potential energy surface of Cp2Pd2(BO)2 is found to be relatively complicated with 11 structures within 20 kcal/mol (MPW1PW91) or 26 kcal/mol (BP86) of the global minimum. This cornucopia of Cp2Pd 2(BO)2 structures includes both perpendicular and coaxial structures exhibiting a variety of different coordination modes of the BO groups. These Cp2Pd2(BO)2 structures even include several structures with the BO group directly bonded to a Cp carbon atom. The Cp2Pd2(BF)2 potential surface is considerably simpler than that of Cp2Pd2(BO)2. Thus a coaxial Cp2Pd2(μ-BF)2 structure with bridging BF groups and a Pd-Pd single bond of ∼2.67 {\AA} is highly favored, lying more than 18 kcal/mol below any of the next lowest energy Cp 2Pd2(BF)2 structures. This Cp 2Pd2(μ-BF)2 structure is closely related to the known structure of the stable compound (η5-M e5C5)2Pd2(μ-CO)2, which has been structurally characterized by X-ray crystallography.",

keywords = "Boronyl, Cyclopentadienyl, Density functional theory, Fluoroborylene, Metal-metal bonding, Palladium",

author = "Hongxia Zhao and Aiping Peng and Xiuhui Zhang and Li, \{Qian Shu\} and King, \{R. Bruce\}",

year = "2013",

doi = "10.1016/j.ica.2013.04.043",

language = "English",

volume = "406",

pages = "285--292",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - The versatility of the boronyl (BO) and fluoroborylene (BF) ligands in binuclear cyclopentadienylpalladium chemistry

AU - Zhao, Hongxia

AU - Peng, Aiping

AU - Zhang, Xiuhui

AU - Li, Qian Shu

AU - King, R. Bruce

PY - 2013

Y1 - 2013

N2 - The organometallic compounds Cp2Pd2(BO)2 and Cp2Pd2(BF)2 have been investigated by the MPW1PW91 and BP86 density functional methods. The potential energy surface of Cp2Pd2(BO)2 is found to be relatively complicated with 11 structures within 20 kcal/mol (MPW1PW91) or 26 kcal/mol (BP86) of the global minimum. This cornucopia of Cp2Pd 2(BO)2 structures includes both perpendicular and coaxial structures exhibiting a variety of different coordination modes of the BO groups. These Cp2Pd2(BO)2 structures even include several structures with the BO group directly bonded to a Cp carbon atom. The Cp2Pd2(BF)2 potential surface is considerably simpler than that of Cp2Pd2(BO)2. Thus a coaxial Cp2Pd2(μ-BF)2 structure with bridging BF groups and a Pd-Pd single bond of ∼2.67 Å is highly favored, lying more than 18 kcal/mol below any of the next lowest energy Cp 2Pd2(BF)2 structures. This Cp 2Pd2(μ-BF)2 structure is closely related to the known structure of the stable compound (η5-M e5C5)2Pd2(μ-CO)2, which has been structurally characterized by X-ray crystallography.

AB - The organometallic compounds Cp2Pd2(BO)2 and Cp2Pd2(BF)2 have been investigated by the MPW1PW91 and BP86 density functional methods. The potential energy surface of Cp2Pd2(BO)2 is found to be relatively complicated with 11 structures within 20 kcal/mol (MPW1PW91) or 26 kcal/mol (BP86) of the global minimum. This cornucopia of Cp2Pd 2(BO)2 structures includes both perpendicular and coaxial structures exhibiting a variety of different coordination modes of the BO groups. These Cp2Pd2(BO)2 structures even include several structures with the BO group directly bonded to a Cp carbon atom. The Cp2Pd2(BF)2 potential surface is considerably simpler than that of Cp2Pd2(BO)2. Thus a coaxial Cp2Pd2(μ-BF)2 structure with bridging BF groups and a Pd-Pd single bond of ∼2.67 Å is highly favored, lying more than 18 kcal/mol below any of the next lowest energy Cp 2Pd2(BF)2 structures. This Cp 2Pd2(μ-BF)2 structure is closely related to the known structure of the stable compound (η5-M e5C5)2Pd2(μ-CO)2, which has been structurally characterized by X-ray crystallography.

KW - Boronyl

KW - Cyclopentadienyl

KW - Density functional theory

KW - Fluoroborylene

KW - Metal-metal bonding

KW - Palladium

UR - https://www.scopus.com/pages/publications/84885326926

U2 - 10.1016/j.ica.2013.04.043

DO - 10.1016/j.ica.2013.04.043

M3 - Article

AN - SCOPUS:84885326926

SN - 0020-1693

VL - 406

SP - 285

EP - 292

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

The versatility of the boronyl (BO) and fluoroborylene (BF) ligands in binuclear cyclopentadienylpalladium chemistry

Abstract

Keywords

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