The Mo-Mo Quintuple Bond as a Ligand to Stabilize Transition-Metal Complexes

Duan-Yen Lu; Peter P-Y Chen; Ting-Shen Kuo; Yi-Chou Tsai

doi:10.1002/anie.201504414

The Mo-Mo Quintuple Bond as a Ligand to Stabilize Transition-Metal Complexes

Angew Chem Int Ed Engl. 2015 Jul 27;54(31):9106-10. doi: 10.1002/anie.201504414. Epub 2015 Jun 26.

Authors

Duan-Yen Lu¹, Peter P-Y Chen², Ting-Shen Kuo³, Yi-Chou Tsai⁴

Affiliations

¹ Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences and Matters, National Tsing Hua University, 101, Sec. 2, Guang-Fu Road, Hsinchu 300 (Taiwan).
² Department of Chemistry, National Chung Hsing University, 250, Kuo-Kuang Road, Taichung 402 (Taiwan).
³ Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Ting-Chow Rd, Taipei 116 (Taiwan).
⁴ Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences and Matters, National Tsing Hua University, 101, Sec. 2, Guang-Fu Road, Hsinchu 300 (Taiwan). [email protected].

PMID: 26118772
DOI: 10.1002/anie.201504414

Abstract

Herein, we report the employment of the Mo-Mo quintuple bonded amidinate complex to stabilize Group 10 metal fragments {(Et3P)2M} (M=Pd, Pt) and give rise to the isolation of the unprecedented δ complexes. X-ray analysis unambiguously revealed short contacts between Pd or Pt and two Mo atoms and a slight elongation of the Mo-Mo quintuple bond in these two compounds. Computational studies show donation of the Mo-Mo quintuple-bond δ electrons to an empty σ orbital on Pd or Pt, and back-donation from a filled Pd or Pt dπ orbital into the Mo-Mo δ* level (LUMO), consistent with the Dewar-Chatt-Duncanson model.

Keywords: Group 10 metals; bonding; molybdenum; δ-bond; δ-complex.