Metathesis by Partner Interchange in σ‐Bond Ligands: Expanding Applications of the σ‐CAM Mechanism

Perutz, Robin N.; Sabo-Étienne, Sylviane; Weller, Andrew S.

doi:10.1002/ange.202111462

“…Are such complexes important? The alkane complexes have acted as paradigms for the development of σ-bond complexes, 151 while the Cr(CO) 5 Xe and Fe(CO) 4 Xe were the first examples of the metal–Ng bond. These complexes also have a role in synthesis since they prolong the lifetime of the reaction intermediates giving them sufficient time to react with solutes that may be present in lower concentrations.…”

Section: Applications To Synthesis Of Complexes With Labile Ligandsmentioning

confidence: 99%

Photochemistry of transition metal carbonyls

Turner

¹

,

George

²

,

Poliakoff

³

et al. 2022

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Reversible Dihydrogen Activation and Catalytic H/D Exchange with Group 10 Heterometallic Complexes**

Garçon

¹

,

Phanopoulos

²

,

White

³

et al. 2022

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Reaction of a hexagonal planar palladium complex featuring a [PdMg 3 H 3 ] core with H 2 is reversible and leads to the formation of a new [PdMg 2 H 4 ] tetrahydride species alongside an equivalent of a magnesium hydride co-product [MgH]. While the reversibility of this process prevented isolation of [PdMg 2 H 4 ], analogous [PtMg 2 H 4 ] and [PtZn 2 H 4 ] complexes could be isolated and characterised through independent syntheses. Computational analysis (DFT, AIM, NCIPlot) of the bonding in a series of heterometallic tetrahydride compounds (Ni-Pt; Mg and Zn) suggests that these complexes are best described as square planar with marginal metal-metal interactions; the strength of which increases slightly as group 10 is descended and increases from Mg to Zn. DFT calculations support a mechanism for H 2 activation involving a ligand-assisted oxidative addition to Pd. These findings were exploited to develop a catalytic protocol for H/D exchange into magnesium hydride and zinc hydride bonds.

show abstract

Reversible Dihydrogen Activation and Catalytic H/D Exchange with Group 10 Heterometallic Complexes**

Garçon

¹

,

Phanopoulos

²

,

White

³

et al. 2022

View full text Add to dashboard Cite

Reaction of a hexagonal planar palladium complex featuring a [PdMg 3 H 3 ] core with H 2 is reversible and leads to the formation of a new [PdMg 2 H 4 ] tetrahydride species alongside an equivalent of a magnesium hydride co-product [MgH]. While the reversibility of this process prevented isolation of [PdMg 2 H 4 ], analogous [PtMg 2 H 4 ] and [PtZn 2 H 4 ] complexes could be isolated and characterised through independent syntheses. Computational analysis (DFT, AIM, NCIPlot) of the bonding in a series of heterometallic tetrahydride compounds (Ni-Pt; Mg and Zn) suggests that these complexes are best described as square planar with marginal metal-metal interactions; the strength of which increases slightly as group 10 is descended and increases from Mg to Zn. DFT calculations support a mechanism for H 2 activation involving a ligand-assisted oxidative addition to Pd. These findings were exploited to develop a catalytic protocol for H/D exchange into magnesium hydride and zinc hydride bonds.

show abstract

Metathesis by Partner Interchange in σ‐Bond Ligands: Expanding Applications of the σ‐CAM Mechanism

Abstract: Scheme 2. Possible coordination modes of methane as s-bond complexes and comparison to agostic interaction with corresponding nomenclature.Scheme 3. Dynamic processes of s-complexes.

Cited by 6 publications

References 164 publications

Photochemistry of transition metal carbonyls

Photochemistry of transition metal carbonyls

Reversible Dihydrogen Activation and Catalytic H/D Exchange with Group 10 Heterometallic Complexes**

Reversible Dihydrogen Activation and Catalytic H/D Exchange with Group 10 Heterometallic Complexes**

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