Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum DOI Creative Commons

Rikiya Matsumoto,

Koichi Nagata, Ryo Nakamura

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(24), P. 5974 - 5974

Published: Dec. 18, 2024

Dihydrogen activation by metallogermylenes was investigated experimentally and theoretically. A neutral NHC-coordinated chlorometallogermylene synthesized converted to a cationic base-free metallogermylene of molybdenum via chloride abstraction. The molybdogermylene showed enhanced reactivity toward H2 compared the tungsten analog. reaction mechanism theoretical calculations, which revealed novel route that proceeds new type metal–ligand cooperative between metal divalent germanium moiety. energy this is much lower than alternative an “oxidative addition” on single Ge(II) center, generally proposed for organotetrylenes. features frontier orbitals origin effect are also described.

Language: Английский

Synthesis and Reactivity of an Iron–Tin Complex with Adjacent Stannylidyne and Ferriostannylene Units DOI Creative Commons
Yang Liu, Franz F. Westermair,

Isabelle Becker

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Heavier transition metal carbyne analogs hold significant potential for cooperative activation of small molecules. However, complexes containing more than one heavier tetrylidyne ligand RE (E = Si, Ge, Sn, Pb) are rare due to the high oligomerization tendency ligands. In this study, we describe complex [Fe(SnAr')2] (1; Ar' 2,6-Dipp2-C6H3, Dipp 2,6-iPr2–C6H3), which features adjacent Fe–Sn single and double bonds. Complex 1 exhibits versatile reactivity with main group compounds. Treatment Ni(COD)2 (COD 1,5-cyclooctadiene) yields tetranuclear [Fe(μ-SnAr')2Ni] (2), characterized by an unusual "push–pull" interaction between nickel(0) two coordinating Sn atoms, as revealed quantum chemical studies. The reaction AlBr3 results in Al–Br bond cleavage migration aluminum. CH3I adds oxidatively atom that is singly bonded Fe, while PMe3 coordinates inducing reversible Fe═Sn bond. addition, activates inorganic CO2 undergoes disproportionation produce a carbonate-bridged Ar'Sn(μ–OCO2)SnAr' ligand, whereas CS2 reductively coupled form ethylene tetrathiolate ([C2S4]4–). white phosphorus (P4) generates Ar'P4Sn2Ar' ligand. This multifaceted illustrates behavior Fe sites 1, suggesting type promising reagents molecule activation.

Language: Английский

Citations

0
Comparative Study of the Structures and Reactivities of Cationic Nickel and Palladium Complexes with a Bismuth-Bisphosphine (PBiP) Ligand DOI Creative Commons
Kent S. Gates,

Yuka Aoyama,

Hang Cao

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Language: Английский

Citations

0
Oxidative addition reactions of heavy analogs of carbenes (germylenes, stannylenes, plumbylenes) to σ-bonds DOI
Elena N. Nikolaevskaya, Mikhail A. Syroeshkin, Mikhail P. Egorov

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 530, P. 216469 - 216469

Published: Feb. 3, 2025

Language: Английский

Citations

0
Catalytic acceptorless dehydrogenation of alcohols using cobalt(i) pincer complexes supported by a P–GeH–P ligand DOI
Yu‐Chao Liu, Danyan Cao,

Qi-Yang Ban

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We report a novel P–GeH–P pincer ligand and its cobalt( i ) complex, which catalyzes the acceptorless dehydrogenation of alcohols.

Language: Английский

Citations

0
Discrete Metal Clusters Supported by Heavier Group-14-Element Ligands DOI Creative Commons
Yusuke Sunada

Coordination chemistry research., Journal Year: 2025, Volume and Issue: unknown, P. 100007 - 100007

Published: May 1, 2025

Language: Английский

Citations

0
Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum DOI Creative Commons

Rikiya Matsumoto,

Koichi Nagata, Ryo Nakamura

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(24), P. 5974 - 5974

Published: Dec. 18, 2024

Dihydrogen activation by metallogermylenes was investigated experimentally and theoretically. A neutral NHC-coordinated chlorometallogermylene synthesized converted to a cationic base-free metallogermylene of molybdenum via chloride abstraction. The molybdogermylene showed enhanced reactivity toward H2 compared the tungsten analog. reaction mechanism theoretical calculations, which revealed novel route that proceeds new type metal–ligand cooperative between metal divalent germanium moiety. energy this is much lower than alternative an “oxidative addition” on single Ge(II) center, generally proposed for organotetrylenes. features frontier orbitals origin effect are also described.

Language: Английский

Citations

0