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Metal–Ligand Cooperation as Key in Formation of Dearomatized NiII–H Pincer Complexes and in Their Reactivity toward CO and CO2
| Content Provider | Semantic Scholar |
|---|---|
| Author | Oren, Dror Diskin-Posner, Yael Avram, Liat Feller, Moran Milstein, David |
| Copyright Year | 2018 |
| Abstract | The unique synthesis and reactivity of [(RPNP*)NiH] complexes (1a,b), based on metal-ligand cooperation (MLC), are presented (RPNP* = deprotonated PNP ligand, R = iPr, tBu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [(RPNP)Ni(MeCN)](BF4)2 with sodium amalgam or by reaction of the free ligand with Ni0(COD)2. Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO2 via MLC to form a rare example of η1 binding of CO2 to nickel, complexes 4a,b. An unusual CO2 cleavage process by complex 4b, involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex 3b and to the new complex [(PiPr2NC2O2)Ni(P(O)iPr2)] (5b). All complexes have been fully characterized by NMR and X-ray crystallography. |
| Starting Page | 2217 |
| Ending Page | 2221 |
| Page Count | 5 |
| File Format | PDF HTM / HTML |
| DOI | 10.1021/acs.organomet.8b00160 |
| PubMed reference number | 31080304 |
| Journal | Medline |
| Volume Number | 37 |
| Alternate Webpage(s) | http://www.weizmann.ac.il/Organic_Chemistry/milstein/sites/Organic_Chemistry.milstein/files/uploads/om8b00160_just_accepted.pdf |
| Alternate Webpage(s) | https://www.armchemfront.com/2018/abstracts/ACF2018_PS151_Oren.pdf |
| Alternate Webpage(s) | https://doi.org/10.1021/acs.organomet.8b00160 |
| Journal | Organometallics |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
