Zero-valent isocyanides of nickel, palladium and platinum as transition metal σ-type Lewis bases
Transition metal complexes that contain metal-to-ligand retrodative σ-bonds have become the subject of increasing studies over the last decade. Lewis acidic "Z-type ligands" can modulate the electronic structure of their resultant complexes in a manner distinct from 2e − donor ligands, and...
Saved in:
| Published in | Chemical communications (Cambridge, England) Vol. 52; no. 96; pp. 13829 - 13839 |
|---|---|
| Main Authors | , |
| Format | Journal Article |
| Language | English |
| Published |
England
24.11.2016
|
| Subjects | |
| Online Access | Get full text |
Cover
Loading…
| Summary: | Transition metal complexes that contain metal-to-ligand retrodative σ-bonds have become the subject of increasing studies over the last decade. Lewis acidic "Z-type ligands" can modulate the electronic structure of their resultant complexes in a manner distinct from 2e
−
donor ligands, and can also engage in cooperative reactivity with a Lewis basic transition metal. In this Feature article, we summarize our work with transition metal isocyanide complexes of group 10 metals that have exploited metal-based σ-type Lewis basicity. While the complexes Ni(CNAr
Mes2
)
3
, Pd(CNAr
Dipp2
)
2
and Pt(CNAr
Dipp2
)
2
were initially targeted as analogues to unstable, low-coordinate metal carbonyls, it soon became apparent that these zero-valent metal centers bore appreciable Lewis basic qualities due largely to the enhanced σ-donor/π-acid ratio of isocyanides compared to CO. Detailed spectroscopic and structural studies of metal-only Lewis pairs (MOLPs) formed from these complexes have furthered our understanding of the electronic structure perturbations effected by Z-type ligand binding. In addition, the platinum (boryl)iminomethane (BIM) complex Pt(κ
2
-N,B-
Cy
2
BIM)(CNAr
Dipp2
) has illuminated a general ligand design strategy that can engender significant reverse-dative interactions with buttressed Lewis acids, and also has expanded the known scope of cooperative reactivity that can be realized at a transition metal-borane linkage.
Transition metal complexes that contain metal-to-ligand retrodative σ-bonds have become the subject of increasing studies over the last decade. |
|---|---|
| Bibliography: | Joshua S. Figueroa grew up in New York City and received his BS degree in chemistry from the University of Delaware in 2000. He completed his graduate studies at the Massachusetts Institute of Technology in 2005 under the direction of Christopher (Kit) C. Cummins and was an NIH postdoctoral fellow from 2005-2007 in the laboratory of Gerard (Ged) Parkin at Columbia University. In July 2007, he started his independent career at the University of California, San Diego (UCSD) with a research program focused on the synthesis, structure and reactivity of unique inorganic and organometallic compounds. Brandon R. Barnett graduated with a BS in Chemistry (Summa Cum Laude) from Pepperdine University in 2011, where he worked in the organometallic research laboratory of Prof. Joseph M. Fritsch. Upon graduation, he began graduate studies at the University of California, San Diego in the group of Prof. Joshua S. Figueroa. As both a NSF Graduate Research Fellow and a U.S. Department of Education GAANN Fellow, Brandon was awarded his PhD in 2016 for work exploring fundamental reactivity studies of platinum and palladium complexes supported by m-terphenyl isocyanides, with particular emphases on transition metal Lewis basicity and ligand-based redox non-innocence. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1359-7345 1364-548X 1364-548X |
| DOI: | 10.1039/c6cc07863j |