Cationic Manganese(I) Dihydrogen and Dinitrogen Complexes Derived from a Formally 16-Electron Complex with a Bis-Agostic Interaction, [Mn(CO)(Ph2PC2H4PPh2)2]+

King, Wayne A.; Luo, Xiao‐Liang; Scott, Brian L.; Kubas, Gregory J.; Zilm, Kurt W.

doi:10.1021/ja960499q

Cited by 88 publications

(54 citation statements)

References 21 publications

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“…19, 28 The standard Gibbs free energy for the transformation from the open configuration to the agnostic configuration was also calculated from the vibrational analysis, and was found to be Δ G ∘ = −39.6 kJ/mol, similar to values found for other agostic interactions. 12 …”

Section: Resultssupporting

confidence: 54%

“…al. 19 Removal of adducts and toluene was performed under high vacuum conditions at 373K until no additional toluene was observable by residual gas mass spectroscopy, producing the five-coordinate product in 90% purity. 1 H NMR (300MHz) in CD 2 Cl 2 under argon atmosphere: δ 2.78 (s, 8H); 6.20 (s, broad, 8H); 6.95-7.40 (m, 32H); 7.56 (s, 4H); 7.73 (s, 8H).…”

Section: Methodsmentioning

confidence: 99%

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Evaluation of the Thermodynamic Properties of H₂ Binding in Solid State Dihydrogen Complexes [M(η²-H₂)(CO)dppe₂][BArF²⁴] (M = Mn, Tc, Re): An Experimental and First Principles Study

Abrecht

Fultz

2012

J. Phys. Chem. C

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The solid state complex [Mn(CO)dppe2][BArF24] was synthesized and the thermodynamic behavior and properties of the hydrogen absorption reaction to form the dihydrogen complex [Mn(η2-H2)dppe2][BArF24] were measured over the temperature range 313K-373K and pressure range 0–600 torr using the Sieverts method. The absorption behavior was accurately described by Langmuir isotherms, and enthalpy and entropy values of ΔH∘=−52.2 kJ/mol and ΔS∘=−99.6 J/mol-K for the absorption reaction were obtained from the Langmuir equilibrium constant. The observed binding strength was similar to metal hydrides and other organometallic complexes, despite rapid kinetics suggesting a site-binding mechanism similar to physisorption materials. Electronic structure calculations using the LANL2DZ-ECP basis set were performed for hydrogen absorption over the organometallic fragments [M(CO)dppe2]+ (M= Mn, Tc, Re). Langmuir isotherms derived from calculation for absorption onto the manganese fragment successfully simulated both the pressure-composition behavior and thermodynamic properties obtained from experiment. Results from calculations for the substitution of the metal center reproduced qualitative binding strength trends of 5d > 3d > 4d previously reported for the group 6 metals.

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Section: Resultssupporting

confidence: 54%

Section: Methodsmentioning

confidence: 99%

Evaluation of the Thermodynamic Properties of H₂ Binding in Solid State Dihydrogen Complexes [M(η²-H₂)(CO)dppe₂][BArF²⁴] (M = Mn, Tc, Re): An Experimental and First Principles Study

Abrecht

Fultz

2012

J. Phys. Chem. C

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“…[54] Further structures with two agostic interactions without additional hydride ligands have been reported for [RuCl 2 {PPh 2 (2,6-Me 2 C 6 H 3 )} 2 ], [55] [Mn(CO)(dppe) 2 ] + (dppe = Ph 2 PCH 2 CH 2 PPh 2 ), [56] + incorporates dihydrogen, hydride, and agostic ligands. [58] …”

Section: Structures With Two S Ligandsmentioning

confidence: 99%

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

2007

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Complexes in which a sigma-H--E bond (E=H, B, Si, C) acts as a two-electron donor to the metal center are called sigma complexes. Clues that it is possible to interconvert sigma ligands without a change in oxidation state derive from C--H activation reactions effecting isotope exchange and from dynamic rearrangements of sigma complexes (see Frontispiece). Through these pathways, metathesis of M--E bonds can occur at late transition metals. We call this process sigma-complex-assisted metathesis, or sigma-CAM, which is distinct from the familiar sigma-bond metathesis (typical for d(0) metals and requiring no intermediate) and from oxidative-reductive elimination mechanisms (inherently requiring intermediates with changed oxidation states and sometimes involving sigma complexes). There are examples of sigma-CAM mechanisms in catalysis, especially for alkane borylation and isotope exchange of alkanes. It may also occur in silylation and alkene hydrogenation.

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“…For example, a cationic H 2 complex such as [Mn(CO)(dppe) 2 (H 2 )] þ can have remarkably similar properties, for example, d HH , to its isoelectronic neutral analogue, Mo(CO) (dppe) 2 (H 2 ). 150 The lack of reliable correlation of vibrational versus other properties brought about by the three-center bonding also extends to the M--H 2 modes.…”

Section: Nature Of M-h 2 Bonding Delineated By Vibrational Analysismentioning

confidence: 99%

Activation of Molecular Hydrogen

Kubas

Heinekey

2010

Physical Inorganic Chemistry

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Cationic Manganese(I) Dihydrogen and Dinitrogen Complexes Derived from a Formally 16-Electron Complex with a Bis-Agostic Interaction, [Mn(CO)(Ph₂PC₂H₄PPh₂)₂]⁺

Cited by 88 publications

References 21 publications

Evaluation of the Thermodynamic Properties of H₂ Binding in Solid State Dihydrogen Complexes [M(η²-H₂)(CO)dppe₂][BArF²⁴] (M = Mn, Tc, Re): An Experimental and First Principles Study

Evaluation of the Thermodynamic Properties of H₂ Binding in Solid State Dihydrogen Complexes [M(η²-H₂)(CO)dppe₂][BArF²⁴] (M = Mn, Tc, Re): An Experimental and First Principles Study

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

Activation of Molecular Hydrogen

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Cationic Manganese(I) Dihydrogen and Dinitrogen Complexes Derived from a Formally 16-Electron Complex with a Bis-Agostic Interaction, [Mn(CO)(Ph2PC2H4PPh2)2]+

Cited by 88 publications

References 21 publications

Evaluation of the Thermodynamic Properties of H2 Binding in Solid State Dihydrogen Complexes [M(η2-H2)(CO)dppe2][BArF24] (M = Mn, Tc, Re): An Experimental and First Principles Study

Evaluation of the Thermodynamic Properties of H2 Binding in Solid State Dihydrogen Complexes [M(η2-H2)(CO)dppe2][BArF24] (M = Mn, Tc, Re): An Experimental and First Principles Study

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

Activation of Molecular Hydrogen

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Product

Resources

About

Cationic Manganese(I) Dihydrogen and Dinitrogen Complexes Derived from a Formally 16-Electron Complex with a Bis-Agostic Interaction, [Mn(CO)(Ph₂PC₂H₄PPh₂)₂]⁺

Evaluation of the Thermodynamic Properties of H₂ Binding in Solid State Dihydrogen Complexes [M(η²-H₂)(CO)dppe₂][BArF²⁴] (M = Mn, Tc, Re): An Experimental and First Principles Study

Evaluation of the Thermodynamic Properties of H₂ Binding in Solid State Dihydrogen Complexes [M(η²-H₂)(CO)dppe₂][BArF²⁴] (M = Mn, Tc, Re): An Experimental and First Principles Study