Experimental Charge Density and Neutron Structural Study of cis-HMn(CO)4PPh3: Comprehensive Analysis of Chemical Bonding and Evidence for a C-H⋯H-Mn Hydrogen Bond

Yuriy A. Abramov, Lee Brammer, Wim T. Klooster, R Morris Bullock

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

The structure and bonding in cis-HMn(CO)4PPh3 have been studied by low-temperature neutron and high-resolution X-ray diffraction, the latter study using a charge-coupled device (CCD) area detector. A charge density analysis, including the deformation density, a full topological analysis of ρ, and selected topological analysis of -▽2ρ, has been conducted, cis-HMn(CO)4PPh3 adopts an approximately octahedral geometry, the largest deviation being the C(1)-Mn-C(3) angle of 160.0(1)°. The hydride ligand (Mn-H(1), 1.573(2) Å) is nucleophilic in nature (i.e., hydridic, with an effective atomic charge of -0.4e) and makes a short contact (2.101(3) Å) with an electrophilic (+0.3e) ortho phenyl hydrogen. The electrostatic component of the Hδ+⋯Hδ- interaction energy is calculated to be 5.7 kcal/mol from the experimental data. This electrostatic evidence coupled with the geometry (C-H⋯H 129.0(2)° and H⋯H-Mn 126.5(1)°) and the identification of an H⋯H bond path in the charge density distribution strongly supports the characterization of this interaction as an intramolecular C-H⋯H-Mn hydrogen bond. Both the deformation density and the topological study clearly illustrate the σ-donor nature of both the H-Mn and Ph3P-Mn interactions and the σ-donor/π-acceptor nature of the manganese-carbonyl bonds. The topological study further confirms the decrease in C-O bond order upon coordination to the metal and demonstrates for the first time by this method that the metal-ligand bonds, although showing characteristics of a closed-shell interaction, do have a significant dative covalent component to the bond. The latter is reinforced by a study of the derived Mn d-orbital populations, in which populations of the dz2 and dx2-y2 orbitals are significantly higher than would be predicted by a simple crystal field theory model of metal-ligand bonding.

Original languageEnglish
Pages (from-to)6317-6328
Number of pages12
JournalInorganic Chemistry
Volume37
Issue number24
Publication statusPublished - 1998

Fingerprint

Carbon Monoxide
Charge density
Hydrogen bonds
Neutrons
Metals
hydrogen bonds
Ligands
neutrons
Electrostatics
ligands
Geometry
interactions
metals
electrostatics
Manganese
Charge coupled devices
Hydrides
orbitals
Hydrogen
geometry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Experimental Charge Density and Neutron Structural Study of cis-HMn(CO)4PPh3 : Comprehensive Analysis of Chemical Bonding and Evidence for a C-H⋯H-Mn Hydrogen Bond. / Abramov, Yuriy A.; Brammer, Lee; Klooster, Wim T.; Bullock, R Morris.

In: Inorganic Chemistry, Vol. 37, No. 24, 1998, p. 6317-6328.

Research output: Contribution to journalArticle

@article{e8e4a18b95324d099ea9d0c7d529d7e8,
title = "Experimental Charge Density and Neutron Structural Study of cis-HMn(CO)4PPh3: Comprehensive Analysis of Chemical Bonding and Evidence for a C-H⋯H-Mn Hydrogen Bond",
abstract = "The structure and bonding in cis-HMn(CO)4PPh3 have been studied by low-temperature neutron and high-resolution X-ray diffraction, the latter study using a charge-coupled device (CCD) area detector. A charge density analysis, including the deformation density, a full topological analysis of ρ, and selected topological analysis of -▽2ρ, has been conducted, cis-HMn(CO)4PPh3 adopts an approximately octahedral geometry, the largest deviation being the C(1)-Mn-C(3) angle of 160.0(1)°. The hydride ligand (Mn-H(1), 1.573(2) {\AA}) is nucleophilic in nature (i.e., hydridic, with an effective atomic charge of -0.4e) and makes a short contact (2.101(3) {\AA}) with an electrophilic (+0.3e) ortho phenyl hydrogen. The electrostatic component of the Hδ+⋯Hδ- interaction energy is calculated to be 5.7 kcal/mol from the experimental data. This electrostatic evidence coupled with the geometry (C-H⋯H 129.0(2)° and H⋯H-Mn 126.5(1)°) and the identification of an H⋯H bond path in the charge density distribution strongly supports the characterization of this interaction as an intramolecular C-H⋯H-Mn hydrogen bond. Both the deformation density and the topological study clearly illustrate the σ-donor nature of both the H-Mn and Ph3P-Mn interactions and the σ-donor/π-acceptor nature of the manganese-carbonyl bonds. The topological study further confirms the decrease in C-O bond order upon coordination to the metal and demonstrates for the first time by this method that the metal-ligand bonds, although showing characteristics of a closed-shell interaction, do have a significant dative covalent component to the bond. The latter is reinforced by a study of the derived Mn d-orbital populations, in which populations of the dz2 and dx2-y2 orbitals are significantly higher than would be predicted by a simple crystal field theory model of metal-ligand bonding.",
author = "Abramov, {Yuriy A.} and Lee Brammer and Klooster, {Wim T.} and Bullock, {R Morris}",
year = "1998",
language = "English",
volume = "37",
pages = "6317--6328",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Experimental Charge Density and Neutron Structural Study of cis-HMn(CO)4PPh3

T2 - Comprehensive Analysis of Chemical Bonding and Evidence for a C-H⋯H-Mn Hydrogen Bond

AU - Abramov, Yuriy A.

AU - Brammer, Lee

AU - Klooster, Wim T.

AU - Bullock, R Morris

PY - 1998

Y1 - 1998

N2 - The structure and bonding in cis-HMn(CO)4PPh3 have been studied by low-temperature neutron and high-resolution X-ray diffraction, the latter study using a charge-coupled device (CCD) area detector. A charge density analysis, including the deformation density, a full topological analysis of ρ, and selected topological analysis of -▽2ρ, has been conducted, cis-HMn(CO)4PPh3 adopts an approximately octahedral geometry, the largest deviation being the C(1)-Mn-C(3) angle of 160.0(1)°. The hydride ligand (Mn-H(1), 1.573(2) Å) is nucleophilic in nature (i.e., hydridic, with an effective atomic charge of -0.4e) and makes a short contact (2.101(3) Å) with an electrophilic (+0.3e) ortho phenyl hydrogen. The electrostatic component of the Hδ+⋯Hδ- interaction energy is calculated to be 5.7 kcal/mol from the experimental data. This electrostatic evidence coupled with the geometry (C-H⋯H 129.0(2)° and H⋯H-Mn 126.5(1)°) and the identification of an H⋯H bond path in the charge density distribution strongly supports the characterization of this interaction as an intramolecular C-H⋯H-Mn hydrogen bond. Both the deformation density and the topological study clearly illustrate the σ-donor nature of both the H-Mn and Ph3P-Mn interactions and the σ-donor/π-acceptor nature of the manganese-carbonyl bonds. The topological study further confirms the decrease in C-O bond order upon coordination to the metal and demonstrates for the first time by this method that the metal-ligand bonds, although showing characteristics of a closed-shell interaction, do have a significant dative covalent component to the bond. The latter is reinforced by a study of the derived Mn d-orbital populations, in which populations of the dz2 and dx2-y2 orbitals are significantly higher than would be predicted by a simple crystal field theory model of metal-ligand bonding.

AB - The structure and bonding in cis-HMn(CO)4PPh3 have been studied by low-temperature neutron and high-resolution X-ray diffraction, the latter study using a charge-coupled device (CCD) area detector. A charge density analysis, including the deformation density, a full topological analysis of ρ, and selected topological analysis of -▽2ρ, has been conducted, cis-HMn(CO)4PPh3 adopts an approximately octahedral geometry, the largest deviation being the C(1)-Mn-C(3) angle of 160.0(1)°. The hydride ligand (Mn-H(1), 1.573(2) Å) is nucleophilic in nature (i.e., hydridic, with an effective atomic charge of -0.4e) and makes a short contact (2.101(3) Å) with an electrophilic (+0.3e) ortho phenyl hydrogen. The electrostatic component of the Hδ+⋯Hδ- interaction energy is calculated to be 5.7 kcal/mol from the experimental data. This electrostatic evidence coupled with the geometry (C-H⋯H 129.0(2)° and H⋯H-Mn 126.5(1)°) and the identification of an H⋯H bond path in the charge density distribution strongly supports the characterization of this interaction as an intramolecular C-H⋯H-Mn hydrogen bond. Both the deformation density and the topological study clearly illustrate the σ-donor nature of both the H-Mn and Ph3P-Mn interactions and the σ-donor/π-acceptor nature of the manganese-carbonyl bonds. The topological study further confirms the decrease in C-O bond order upon coordination to the metal and demonstrates for the first time by this method that the metal-ligand bonds, although showing characteristics of a closed-shell interaction, do have a significant dative covalent component to the bond. The latter is reinforced by a study of the derived Mn d-orbital populations, in which populations of the dz2 and dx2-y2 orbitals are significantly higher than would be predicted by a simple crystal field theory model of metal-ligand bonding.

UR - http://www.scopus.com/inward/record.url?scp=0000895394&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000895394&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000895394

VL - 37

SP - 6317

EP - 6328

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 24

ER -