A new ONO(3-) trianionic pincer ligand with intermediate flexibility and its tungsten alkylidene and alkylidyne complexes
This report details the synthesis and characterization of the semi-flexible [ON(CH2)O]H3 (1) ligand and its W(vi)-alkylidene and alkylidyne complexes. The alkylidyne complex [ONH(CH2)O]W[triple bond, length as m-dash]C(t)Bu(O(t)Bu) (2) forms as a result of alcoholysis of 1 with ((t)BuO)3W[triple bond, length as m-dash]C(t)Bu. Complex 2 evolves to [ON(CH2)O]W[double bond, length as m-dash]CH(t)Bu(O(t)Bu) (3) through proton migration from the N atom of the pincer ligand to the W[triple bond, length as m-dash]Cα bond. Deprotonation of 2 or 3 with Ph3PCH2 affords the anionic alkylidyne {CH3PPh3}{[ON(CH2)O]W[triple bond, length as m-dash]C(t)Bu(O(t)Bu)} (4). Complex 4 exhibits pincer-ligand-centered reactivity with electrophiles (H(+), Me(+), and TMS(+)), in spite of its enhanced inorganic enamine interaction. Addition of 2 equiv. of HCl to 4 yields the W(vi)-neopentyl complex [ON(CH2)O]W(CH2(t)Bu)(O(t)Bu)(Cl) (5). MeOTf or TMSOTf addition to 4 generates the dianionic pincer ligated alkylidynes [ONR(CH2)O]W[triple bond, length as m-dash]C(t)Bu(O(t)Bu) (R = Me (6-Me); TMS (6-TMS)). Complexes 2-5 were characterized by multinuclear NMR spectroscopy, and combustion analysis. Complexes 4 and 5 were also characterized by single crystal X-ray diffraction. This work bridges the gap in the series involving W(vi)-alkylidynes ligated to the rigid [CF3-ONO](3-), and the flexible [O(CH2)N(CH2)O](3-) ligands. DFT computations permit comparison of the inorganic enamine effect within alkylidynes supported by all three trianionic-pincer type ONO ligands.
| Medienart: |
E-Artikel |
|---|
| Erscheinungsjahr: |
2015 |
|---|---|
| Erschienen: |
2015 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:44 |
|---|---|
| Enthalten in: |
Dalton transactions (Cambridge, England : 2003) - 44(2015), 42 vom: 14. Nov., Seite 18475-86 |
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
VenkatRamani, Sudarsan [VerfasserIn] |
|---|
| Links: |
|---|
| Themen: |
Coordination Complexes |
|---|
| Anmerkungen: |
Date Completed 22.07.2016 Date Revised 21.10.2015 published: Print-Electronic Citation Status MEDLINE |
|---|
| doi: |
10.1039/c5dt02911b |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
NLM253473446 |
|---|
| LEADER | 01000naa a22002652 4500 | ||
|---|---|---|---|
| 001 | NLM253473446 | ||
| 003 | DE-627 | ||
| 005 | 20231224170308.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 231224s2015 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1039/c5dt02911b |2 doi | |
| 028 | 5 | 2 | |a pubmed24n0844.xml |
| 035 | |a (DE-627)NLM253473446 | ||
| 035 | |a (NLM)26445231 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a VenkatRamani, Sudarsan |e verfasserin |4 aut | |
| 245 | 1 | 2 | |a A new ONO(3-) trianionic pincer ligand with intermediate flexibility and its tungsten alkylidene and alkylidyne complexes |
| 264 | 1 | |c 2015 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ƒaComputermedien |b c |2 rdamedia | ||
| 338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Date Completed 22.07.2016 | ||
| 500 | |a Date Revised 21.10.2015 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a This report details the synthesis and characterization of the semi-flexible [ON(CH2)O]H3 (1) ligand and its W(vi)-alkylidene and alkylidyne complexes. The alkylidyne complex [ONH(CH2)O]W[triple bond, length as m-dash]C(t)Bu(O(t)Bu) (2) forms as a result of alcoholysis of 1 with ((t)BuO)3W[triple bond, length as m-dash]C(t)Bu. Complex 2 evolves to [ON(CH2)O]W[double bond, length as m-dash]CH(t)Bu(O(t)Bu) (3) through proton migration from the N atom of the pincer ligand to the W[triple bond, length as m-dash]Cα bond. Deprotonation of 2 or 3 with Ph3PCH2 affords the anionic alkylidyne {CH3PPh3}{[ON(CH2)O]W[triple bond, length as m-dash]C(t)Bu(O(t)Bu)} (4). Complex 4 exhibits pincer-ligand-centered reactivity with electrophiles (H(+), Me(+), and TMS(+)), in spite of its enhanced inorganic enamine interaction. Addition of 2 equiv. of HCl to 4 yields the W(vi)-neopentyl complex [ON(CH2)O]W(CH2(t)Bu)(O(t)Bu)(Cl) (5). MeOTf or TMSOTf addition to 4 generates the dianionic pincer ligated alkylidynes [ONR(CH2)O]W[triple bond, length as m-dash]C(t)Bu(O(t)Bu) (R = Me (6-Me); TMS (6-TMS)). Complexes 2-5 were characterized by multinuclear NMR spectroscopy, and combustion analysis. Complexes 4 and 5 were also characterized by single crystal X-ray diffraction. This work bridges the gap in the series involving W(vi)-alkylidynes ligated to the rigid [CF3-ONO](3-), and the flexible [O(CH2)N(CH2)O](3-) ligands. DFT computations permit comparison of the inorganic enamine effect within alkylidynes supported by all three trianionic-pincer type ONO ligands | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Coordination Complexes |2 NLM | |
| 650 | 7 | |a Ligands |2 NLM | |
| 650 | 7 | |a Tungsten |2 NLM | |
| 650 | 7 | |a V9306CXO6G |2 NLM | |
| 700 | 1 | |a Ghiviriga, Ion |e verfasserin |4 aut | |
| 700 | 1 | |a Abboud, Khalil A |e verfasserin |4 aut | |
| 700 | 1 | |a Veige, Adam S |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Dalton transactions (Cambridge, England : 2003) |d 2004 |g 44(2015), 42 vom: 14. Nov., Seite 18475-86 |w (DE-627)NLM149339739 |x 1477-9234 |7 nnns |
| 773 | 1 | 8 | |g volume:44 |g year:2015 |g number:42 |g day:14 |g month:11 |g pages:18475-86 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1039/c5dt02911b |3 Volltext |
| 912 | |a GBV_USEFLAG_A | ||
| 912 | |a GBV_NLM | ||
| 951 | |a AR | ||
| 952 | |d 44 |j 2015 |e 42 |b 14 |c 11 |h 18475-86 | ||